EUR 23013 EN - 2007

Project HORIZONTAL Validation Reporton specific electrical conductivity

Validation of a horizontal standard for the determination of specific electrical conductivity in soils sludges and treated biowaste

in a European Intercomparison Exercise

E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik

The mission of the Institute for Environment and Sustainability is to provide scientific-technical support to the European Unionrsquos Policies for the protection and sustainable development of the European and global environment European Commission Joint Research Centre Institute for Environment and Sustainability Contact information Address Via Enrico Fermi 2749 21027 Ispra (VA) Italy E-mail berndgawlikjrcit Tel +39 0332 789487 Fax +39 0332 789158 httpiesjrceceuropaeu httpwwwjrceceuropaeu Legal Notice Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be made of this publication A great deal of additional information on the European Union is available on the Internet It can be accessed through the Europa server httpeuropaeu JRC 40202 EUR 23013 EN ISBN 978-92-79-07413-4 ISSN 1018-5593 DOI 10278848128 Luxembourg Office for Official Publications of the European Communities copy European Communities 2007 Reproduction is authorised provided the source is acknowledged Printed in Luxembourg

Project HORIZONTAL Validation Report Validation of a horizontal standard for the determination of specific electrical conductivity (EC) in soils sludge and treated biowaste in a European Intercomparison Exercise E Sobiecka H Van der Sloot I Nilsson P Jennische B M Gawlik Elzbieta Sobiecka Bernd Manfred Gawlik European Commission Joint Research Centre Institute for Environment and Sustainability Via Enrico Fermi 21020 Ispra - Italy

Hans van der Sloot ECN Emission Characterisation and Reduction Westerduinweg 3 PO Box 1 1755 ZG Petten The Netherlands

Ingvar Nilsson Swedish University of Agriculture Sciences (SLU) Department of Soil Sciences PO Box 7014 SE-750 07 Uppsala Sweden

Per Jennische Swedish University of Agriculture Sciences (SLU) Ledningskansliet internationella enh Box 7070 Arrheniusplan 2 C 750 07 UPPSALA Sweden

to whom correspondence should be sent

by email to berndgawlikjrcit

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using conductometric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

EC Electrical conductivity

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

MILC Measure Interlaboratory Comparison

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents

Summary 2

Abbreviations 3

Table of Contents 4

Introduction to the validation project 5

11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6

112 Requirements for precision experiment 7

113 Statistical analysis 8

12 Validation exercise for electrical conductivity 9

121 Samples dispatched for the validation of electrical conductivity 9

122 Draft standards to be followed 9

123 Analytical program 9

124 Timing and Submission of data 9

125 Participants 10

13 Summary results and derived performance characteristics 11

14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison1 The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of electrical conductivity (EC) are described hereafter

1 The desk study regarding evaluation of measurements of specific electrical conductivity included only literature research Thus no experimental evaluation was undertaken before the standard was drafted

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the EC draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material2 (3 per bottle) using the respective draft standard methods The 6 analyses per material should be carried out under repeatability conditions (ie same operator3 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

2 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 3 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

9

12 Validation exercise for electrical conductivity

121 Samples dispatched for the validation of electrical conductivity After a preliminary rough screening the following materials were used for the validation round of EC

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalEC_standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for EC to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter

10

In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal EC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Amt der Steirmaumlrkischen Landesregierung o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o University of Natural resources and Applied Life Science

bull Belgium o VITO

bull Finland o Finnish Food safety Authority Evira o VTT

bull France o SAS Laboratoire

bull Germany o Umweltbundesamt o Fachhochschule Weihenstephan Forschungsanstalt fuumlr Gartenbau o Biolab Umweltanalysen GmbH

bull Italy o CRA - Istituto Sperimentale per la Nutrizione delle Piante

bull Sweden o ALCONTROL AB

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

The mission of the Institute for Environment and Sustainability is to provide scientific-technical support to the European Unionrsquos Policies for the protection and sustainable development of the European and global environment European Commission Joint Research Centre Institute for Environment and Sustainability Contact information Address Via Enrico Fermi 2749 21027 Ispra (VA) Italy E-mail berndgawlikjrcit Tel +39 0332 789487 Fax +39 0332 789158 httpiesjrceceuropaeu httpwwwjrceceuropaeu Legal Notice Neither the European Commission nor any person acting on behalf of the Commission is responsible for the use which might be made of this publication A great deal of additional information on the European Union is available on the Internet It can be accessed through the Europa server httpeuropaeu JRC 40202 EUR 23013 EN ISBN 978-92-79-07413-4 ISSN 1018-5593 DOI 10278848128 Luxembourg Office for Official Publications of the European Communities copy European Communities 2007 Reproduction is authorised provided the source is acknowledged Printed in Luxembourg

Project HORIZONTAL Validation Report Validation of a horizontal standard for the determination of specific electrical conductivity (EC) in soils sludge and treated biowaste in a European Intercomparison Exercise E Sobiecka H Van der Sloot I Nilsson P Jennische B M Gawlik Elzbieta Sobiecka Bernd Manfred Gawlik European Commission Joint Research Centre Institute for Environment and Sustainability Via Enrico Fermi 21020 Ispra - Italy

Hans van der Sloot ECN Emission Characterisation and Reduction Westerduinweg 3 PO Box 1 1755 ZG Petten The Netherlands

Ingvar Nilsson Swedish University of Agriculture Sciences (SLU) Department of Soil Sciences PO Box 7014 SE-750 07 Uppsala Sweden

Per Jennische Swedish University of Agriculture Sciences (SLU) Ledningskansliet internationella enh Box 7070 Arrheniusplan 2 C 750 07 UPPSALA Sweden

to whom correspondence should be sent

by email to berndgawlikjrcit

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using conductometric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

EC Electrical conductivity

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

MILC Measure Interlaboratory Comparison

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents

Summary 2

Abbreviations 3

Table of Contents 4

Introduction to the validation project 5

11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6

112 Requirements for precision experiment 7

113 Statistical analysis 8

12 Validation exercise for electrical conductivity 9

121 Samples dispatched for the validation of electrical conductivity 9

122 Draft standards to be followed 9

123 Analytical program 9

124 Timing and Submission of data 9

125 Participants 10

13 Summary results and derived performance characteristics 11

14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison1 The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of electrical conductivity (EC) are described hereafter

1 The desk study regarding evaluation of measurements of specific electrical conductivity included only literature research Thus no experimental evaluation was undertaken before the standard was drafted

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the EC draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material2 (3 per bottle) using the respective draft standard methods The 6 analyses per material should be carried out under repeatability conditions (ie same operator3 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

2 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 3 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

9

12 Validation exercise for electrical conductivity

121 Samples dispatched for the validation of electrical conductivity After a preliminary rough screening the following materials were used for the validation round of EC

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalEC_standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for EC to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter

10

In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal EC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Amt der Steirmaumlrkischen Landesregierung o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o University of Natural resources and Applied Life Science

bull Belgium o VITO

bull Finland o Finnish Food safety Authority Evira o VTT

bull France o SAS Laboratoire

bull Germany o Umweltbundesamt o Fachhochschule Weihenstephan Forschungsanstalt fuumlr Gartenbau o Biolab Umweltanalysen GmbH

bull Italy o CRA - Istituto Sperimentale per la Nutrizione delle Piante

bull Sweden o ALCONTROL AB

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Project HORIZONTAL Validation Report Validation of a horizontal standard for the determination of specific electrical conductivity (EC) in soils sludge and treated biowaste in a European Intercomparison Exercise E Sobiecka H Van der Sloot I Nilsson P Jennische B M Gawlik Elzbieta Sobiecka Bernd Manfred Gawlik European Commission Joint Research Centre Institute for Environment and Sustainability Via Enrico Fermi 21020 Ispra - Italy

Hans van der Sloot ECN Emission Characterisation and Reduction Westerduinweg 3 PO Box 1 1755 ZG Petten The Netherlands

Ingvar Nilsson Swedish University of Agriculture Sciences (SLU) Department of Soil Sciences PO Box 7014 SE-750 07 Uppsala Sweden

Per Jennische Swedish University of Agriculture Sciences (SLU) Ledningskansliet internationella enh Box 7070 Arrheniusplan 2 C 750 07 UPPSALA Sweden

to whom correspondence should be sent

by email to berndgawlikjrcit

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using conductometric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

EC Electrical conductivity

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

MILC Measure Interlaboratory Comparison

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents

Summary 2

Abbreviations 3

Table of Contents 4

Introduction to the validation project 5

11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6

112 Requirements for precision experiment 7

113 Statistical analysis 8

12 Validation exercise for electrical conductivity 9

121 Samples dispatched for the validation of electrical conductivity 9

122 Draft standards to be followed 9

123 Analytical program 9

124 Timing and Submission of data 9

125 Participants 10

13 Summary results and derived performance characteristics 11

14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison1 The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of electrical conductivity (EC) are described hereafter

1 The desk study regarding evaluation of measurements of specific electrical conductivity included only literature research Thus no experimental evaluation was undertaken before the standard was drafted

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the EC draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material2 (3 per bottle) using the respective draft standard methods The 6 analyses per material should be carried out under repeatability conditions (ie same operator3 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

2 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 3 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

9

12 Validation exercise for electrical conductivity

121 Samples dispatched for the validation of electrical conductivity After a preliminary rough screening the following materials were used for the validation round of EC

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalEC_standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for EC to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter

10

In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal EC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Amt der Steirmaumlrkischen Landesregierung o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o University of Natural resources and Applied Life Science

bull Belgium o VITO

bull Finland o Finnish Food safety Authority Evira o VTT

bull France o SAS Laboratoire

bull Germany o Umweltbundesamt o Fachhochschule Weihenstephan Forschungsanstalt fuumlr Gartenbau o Biolab Umweltanalysen GmbH

bull Italy o CRA - Istituto Sperimentale per la Nutrizione delle Piante

bull Sweden o ALCONTROL AB

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

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Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

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ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

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ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

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Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

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ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

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Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

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ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

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Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Summary Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using conductometric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

EC Electrical conductivity

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

MILC Measure Interlaboratory Comparison

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents

Summary 2

Abbreviations 3

Table of Contents 4

Introduction to the validation project 5

11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6

112 Requirements for precision experiment 7

113 Statistical analysis 8

12 Validation exercise for electrical conductivity 9

121 Samples dispatched for the validation of electrical conductivity 9

122 Draft standards to be followed 9

123 Analytical program 9

124 Timing and Submission of data 9

125 Participants 10

13 Summary results and derived performance characteristics 11

14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison1 The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of electrical conductivity (EC) are described hereafter

1 The desk study regarding evaluation of measurements of specific electrical conductivity included only literature research Thus no experimental evaluation was undertaken before the standard was drafted

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the EC draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material2 (3 per bottle) using the respective draft standard methods The 6 analyses per material should be carried out under repeatability conditions (ie same operator3 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

2 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 3 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

9

12 Validation exercise for electrical conductivity

121 Samples dispatched for the validation of electrical conductivity After a preliminary rough screening the following materials were used for the validation round of EC

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalEC_standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for EC to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter

10

In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal EC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Amt der Steirmaumlrkischen Landesregierung o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o University of Natural resources and Applied Life Science

bull Belgium o VITO

bull Finland o Finnish Food safety Authority Evira o VTT

bull France o SAS Laboratoire

bull Germany o Umweltbundesamt o Fachhochschule Weihenstephan Forschungsanstalt fuumlr Gartenbau o Biolab Umweltanalysen GmbH

bull Italy o CRA - Istituto Sperimentale per la Nutrizione delle Piante

bull Sweden o ALCONTROL AB

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Abbreviations Throughout this report the following abbreviations are used ANOVA Analysis of variances

CAS Chemical Abstracts System

CEN Comitteeacute Europeacuteen de Normalisation

DG Directorate General

EC Electrical conductivity

ECN Energy Research Centre for the Netherlands

EU European Union

IES Institute for Environment and Sustainability

IT Information Technology

ISO International Organization for Standardisation

JRC Joint Research Centre

MILC Measure Interlaboratory Comparison

p Number of labs

r Repeatability limit

R Reproducibility limit

sr Repeatability standard deviation

sR Reproducibility standard deviation

TC Technical Committee

4

Table of Contents

Summary 2

Abbreviations 3

Table of Contents 4

Introduction to the validation project 5

11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6

112 Requirements for precision experiment 7

113 Statistical analysis 8

12 Validation exercise for electrical conductivity 9

121 Samples dispatched for the validation of electrical conductivity 9

122 Draft standards to be followed 9

123 Analytical program 9

124 Timing and Submission of data 9

125 Participants 10

13 Summary results and derived performance characteristics 11

14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison1 The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of electrical conductivity (EC) are described hereafter

1 The desk study regarding evaluation of measurements of specific electrical conductivity included only literature research Thus no experimental evaluation was undertaken before the standard was drafted

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the EC draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material2 (3 per bottle) using the respective draft standard methods The 6 analyses per material should be carried out under repeatability conditions (ie same operator3 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

2 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 3 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

9

12 Validation exercise for electrical conductivity

121 Samples dispatched for the validation of electrical conductivity After a preliminary rough screening the following materials were used for the validation round of EC

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalEC_standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for EC to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter

10

In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal EC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Amt der Steirmaumlrkischen Landesregierung o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o University of Natural resources and Applied Life Science

bull Belgium o VITO

bull Finland o Finnish Food safety Authority Evira o VTT

bull France o SAS Laboratoire

bull Germany o Umweltbundesamt o Fachhochschule Weihenstephan Forschungsanstalt fuumlr Gartenbau o Biolab Umweltanalysen GmbH

bull Italy o CRA - Istituto Sperimentale per la Nutrizione delle Piante

bull Sweden o ALCONTROL AB

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

4

Table of Contents

Summary 2

Abbreviations 3

Table of Contents 4

Introduction to the validation project 5

11 Statistical concept underlying the validation 6

111 Introduction to the statistical model 6

112 Requirements for precision experiment 7

113 Statistical analysis 8

12 Validation exercise for electrical conductivity 9

121 Samples dispatched for the validation of electrical conductivity 9

122 Draft standards to be followed 9

123 Analytical program 9

124 Timing and Submission of data 9

125 Participants 10

13 Summary results and derived performance characteristics 11

14 Annexes 13

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison1 The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of electrical conductivity (EC) are described hereafter

1 The desk study regarding evaluation of measurements of specific electrical conductivity included only literature research Thus no experimental evaluation was undertaken before the standard was drafted

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the EC draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material2 (3 per bottle) using the respective draft standard methods The 6 analyses per material should be carried out under repeatability conditions (ie same operator3 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

2 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 3 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

9

12 Validation exercise for electrical conductivity

121 Samples dispatched for the validation of electrical conductivity After a preliminary rough screening the following materials were used for the validation round of EC

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalEC_standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for EC to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter

10

In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal EC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Amt der Steirmaumlrkischen Landesregierung o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o University of Natural resources and Applied Life Science

bull Belgium o VITO

bull Finland o Finnish Food safety Authority Evira o VTT

bull France o SAS Laboratoire

bull Germany o Umweltbundesamt o Fachhochschule Weihenstephan Forschungsanstalt fuumlr Gartenbau o Biolab Umweltanalysen GmbH

bull Italy o CRA - Istituto Sperimentale per la Nutrizione delle Piante

bull Sweden o ALCONTROL AB

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

5

Introduction to the validation project Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes It was created as in response to the European Commission Mandate M 330 given to CEN asking for the development and validation of those standards in support of forthcoming EU Directives such as

o The revision of the Sewage Sludge Directive 86278EEC o The Directive on the biological treatment of biodegradable waste o The initiative on a legal framework for soil monitoring in Europe

This mandate explicitly considers standards for the entire analytical procedure (ie sampling pre-treatment and analytical measurement methods for inorganic organic hygiene and biological parameters) These are grouped into classes according to their physicalchemical properties which in turn determine the methods needed to quantify the potential impact on human and animal health plant uptake soil function and groundwater quality As the materials generally feature a mixture of different types of contaminants it is important to provide an integrated answer covering evaluation of all relevant pollutants In order to fulfil the requirements of the aforementioned mandate the European Commissions Joint Research Centre (JRC) and its Directorate-General for Environment (DG ENV) together with the Technical Committees of the European Standardisation Committee (CEN TCs) concerned designed a pre-normative research initiative called Project HORIZONTAL and presented it to the Commission and the Environmental Authorities in the Member States After an extensive literature research and careful evaluation of the feasibility of a given horizontal standard the standards were drafted and finally validated in a European laboratory intercomparison1 The underlying statistical concept information about the materials used details about the participants measurement results obtained as well as the derived performance characteristics obtained for the determination of electrical conductivity (EC) are described hereafter

1 The desk study regarding evaluation of measurements of specific electrical conductivity included only literature research Thus no experimental evaluation was undertaken before the standard was drafted

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the EC draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material2 (3 per bottle) using the respective draft standard methods The 6 analyses per material should be carried out under repeatability conditions (ie same operator3 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

2 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 3 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

9

12 Validation exercise for electrical conductivity

121 Samples dispatched for the validation of electrical conductivity After a preliminary rough screening the following materials were used for the validation round of EC

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalEC_standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for EC to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter

10

In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal EC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Amt der Steirmaumlrkischen Landesregierung o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o University of Natural resources and Applied Life Science

bull Belgium o VITO

bull Finland o Finnish Food safety Authority Evira o VTT

bull France o SAS Laboratoire

bull Germany o Umweltbundesamt o Fachhochschule Weihenstephan Forschungsanstalt fuumlr Gartenbau o Biolab Umweltanalysen GmbH

bull Italy o CRA - Istituto Sperimentale per la Nutrizione delle Piante

bull Sweden o ALCONTROL AB

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

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Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

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Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

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Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

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Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

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Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

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Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

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Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

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61L

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Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

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Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

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Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

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Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

6

11 Statistical concept underlying the validation According to the requirements of the work package concerning data handling amp interpretation of the project HORIZONTAL-ORG the respective validation intercomparisons have to be evaluated according to the principles laid down in ISO standard 5725-21994 In particular repeatability and reproducibility of the draft standard methods have to be determined The determination of trueness would require the availability of independent reference values for the materials investigated This however is not possible and was not requested in the frame of this work In the following the approach chosen is explained

111 Introduction to the statistical model The statistical model used in ISO 5725 for estimation of accuracy of a measurement method assumes that every test result is the sum of three components

eBmy ++= y test result m general mean B laboratory component of bias under repeatability conditions e random error occurring in every measurement under repeatability conditions

In the workprogram the quantification of term e is explicitly asked for (ie repeatability and reproducibility) The repeatability variance is measured directly as the variance of the error term e but the reproducibility depends on the sum of the repeatability variance and the between-laboratory variance

( )er var=σ 22rLR σσσ += with ( )BL var=σ

However soil biowaste and sludge are multi-phase materials ie they contain two or more distinct types of particles which are fundamentally different in their properties and composition As a consequence this introduces an important source of variation for the intercomparison exercise which needs to be considered ie the inherent heterogeneity of the materials Thus a contribution of variation between samples H is introduced to the general statistical model

HeBmy +++= Using ANOVA techniques the different variances are calculated and separated for the evaluation

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the EC draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material2 (3 per bottle) using the respective draft standard methods The 6 analyses per material should be carried out under repeatability conditions (ie same operator3 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

2 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 3 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

9

12 Validation exercise for electrical conductivity

121 Samples dispatched for the validation of electrical conductivity After a preliminary rough screening the following materials were used for the validation round of EC

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalEC_standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for EC to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter

10

In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal EC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Amt der Steirmaumlrkischen Landesregierung o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o University of Natural resources and Applied Life Science

bull Belgium o VITO

bull Finland o Finnish Food safety Authority Evira o VTT

bull France o SAS Laboratoire

bull Germany o Umweltbundesamt o Fachhochschule Weihenstephan Forschungsanstalt fuumlr Gartenbau o Biolab Umweltanalysen GmbH

bull Italy o CRA - Istituto Sperimentale per la Nutrizione delle Piante

bull Sweden o ALCONTROL AB

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

7

112 Requirements for precision experiment

Layout of the experiment A suite of 10 to 12 different materials (soil sludge and biowaste) has been made available for the intercomparison exercise For each parameter investigated at least 10 to laboratories should be nominated to participate The same laboratories should be used for different parameters as far as possible Due to the complexity of analysis and the respective workload to the laboratories it was decided to propose three materials for the validation of the EC draft standard Each laboratory received two bottles of each material and was be requested to perform 6 independent analyses per material2 (3 per bottle) using the respective draft standard methods The 6 analyses per material should be carried out under repeatability conditions (ie same operator3 same equipment within a short period of time) As far as possible also the different materials should be measured under repeatability conditions however changes of eg operator or equipment are permitted but must be reported Likewise different materials can be analysed on different days if necessary Equipment used in the experiment needed to be checked prior to the experiment according to the requirements of the draft standard The results of these checks have to be documented Similarly date and time of each measurement had to be recorded for verification of repeatability conditions An appropriate timeframe for the entire exercise has been set and was to be respected

Recruitment of the laboratories Each sub-workpackage leader of HORIZONTAL was asked to select the laboratories using the information from section 52 of ISO 5725-21994 and provide the signed questionnaires (see also Annex 1) The workpackage leaders were responsible for providing the laboratories with the draft standard method and explaining the context of this exercise

Preparation and use of the materials Materials used for the exercise were prepared according to the general requirements for reference materials as laid down in ISO Guide 34 Materials were accompanied by instructions for use

Reporting of results Online submissions of results using an internet-based IT platform as well as XLS-Spreadsheets were used In case of online data submission the participating laboratories received a unique and confidential login and password in due time enabling them to

2 Independent analysis means analysis of independent test portions applying the entire analytical scheme to this test portion from eg extraction to quantification For instance it does not mean replicate injections of aliquots into a GC-MS instrument 3 Operator in this context may also consist of a fixed team of persons eg one person performing extraction one clean-up one quantification

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

9

12 Validation exercise for electrical conductivity

121 Samples dispatched for the validation of electrical conductivity After a preliminary rough screening the following materials were used for the validation round of EC

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalEC_standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for EC to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter

10

In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal EC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Amt der Steirmaumlrkischen Landesregierung o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o University of Natural resources and Applied Life Science

bull Belgium o VITO

bull Finland o Finnish Food safety Authority Evira o VTT

bull France o SAS Laboratoire

bull Germany o Umweltbundesamt o Fachhochschule Weihenstephan Forschungsanstalt fuumlr Gartenbau o Biolab Umweltanalysen GmbH

bull Italy o CRA - Istituto Sperimentale per la Nutrizione delle Piante

bull Sweden o ALCONTROL AB

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

8

enter their data in a structured form For authentication purposes a signed printout had to be submitted by mail The online data submission included a detailed questionnaire for additional information on the measurements

113 Statistical analysis Statistical analysis of data followed the requirements of ISO 5725-21994 and ISO 5725-51998 Appropriate tests for the homogeneity of variance detection of outliers and normal distribution were applied Statistical evaluation was done using an Excel Macro developed tested and successfully applied in other occasion by ECN Evaluation was executed jointly by JRC and ECN

9

12 Validation exercise for electrical conductivity

121 Samples dispatched for the validation of electrical conductivity After a preliminary rough screening the following materials were used for the validation round of EC

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalEC_standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for EC to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter

10

In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal EC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Amt der Steirmaumlrkischen Landesregierung o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o University of Natural resources and Applied Life Science

bull Belgium o VITO

bull Finland o Finnish Food safety Authority Evira o VTT

bull France o SAS Laboratoire

bull Germany o Umweltbundesamt o Fachhochschule Weihenstephan Forschungsanstalt fuumlr Gartenbau o Biolab Umweltanalysen GmbH

bull Italy o CRA - Istituto Sperimentale per la Nutrizione delle Piante

bull Sweden o ALCONTROL AB

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

9

12 Validation exercise for electrical conductivity

121 Samples dispatched for the validation of electrical conductivity After a preliminary rough screening the following materials were used for the validation round of EC

bull Compost 1 A pollutant loaded compost material from Vienna bull Compost 2 A pollutant loaded compost materia from Germany bull Sewage Sludge 1 A mixed sewage sludge from Essen Germany bull Sewage Sludge 2 A mixed municipal WWTP sludge from North Rhine

Westphalia Germany bull Soil 4 A sludge amended soil from Hohenheim Germany bull Soil 5 An agricultural soil from Reading UK

A more detailed description of background concentrations can be found in Annex 2 to this report The samples were dispatched simultaneously to all participants using a private courier service

122 Draft standards to be followed The draft standards to be followed could be downloaded following this link which is situated on the website of the Project HORIZONTAL httpwwwecnnldocssocietyhorizontalEC_standard_for_validationpdf

123 Analytical program Of each of the six materials 2 bottles had to be analyzed and each bottle had to analyze independently three times As mentioned above analyses were to be done under repeatability conditions Results were to be reported referring to DRY MATTER content The choice how to apply dm correction was free for each participant

124 Timing and Submission of data Dispatch of samples was done on the 18th of October 2006 For users of the Online data submission system (MILC) User Registration was possible from 14th of November 2006 with opening of the MILC Data Submission on 1st of December 2006 The deadline for submission of results has been set for EC to the 31st of January 2007 After that no further submission was possible Alternatively the participants were allowed to submit data electronically as Excel sheet using simply Email All data were treated in a confidential way Any presentation hereafter will refer only to numerical data and it will not be possible to identify the originating laboratory Lab Codes displayed are NOT related to the order of laboratories hereafter

10

In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal EC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Amt der Steirmaumlrkischen Landesregierung o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o University of Natural resources and Applied Life Science

bull Belgium o VITO

bull Finland o Finnish Food safety Authority Evira o VTT

bull France o SAS Laboratoire

bull Germany o Umweltbundesamt o Fachhochschule Weihenstephan Forschungsanstalt fuumlr Gartenbau o Biolab Umweltanalysen GmbH

bull Italy o CRA - Istituto Sperimentale per la Nutrizione delle Piante

bull Sweden o ALCONTROL AB

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

10

In addition to the information provide a Helpdesk was implemented in order to give quick and individual response to the participants during and immediately after the validation study In case of doubt and suspected transcription errors further enquires were conducted by JRC

125 Participants The following table lists the participating organizations and entities in the validation exercise for the horizontal EC standard

bull Austria o barbara - Engineering Consulting Research amp Service GmbH o Amt der Steirmaumlrkischen Landesregierung o Magistrat der Stadt Wien o NUA Umweltanalytik GmbH o Universitaumlt fuumlr Bodenkultur Wien o University of Natural resources and Applied Life Science

bull Belgium o VITO

bull Finland o Finnish Food safety Authority Evira o VTT

bull France o SAS Laboratoire

bull Germany o Umweltbundesamt o Fachhochschule Weihenstephan Forschungsanstalt fuumlr Gartenbau o Biolab Umweltanalysen GmbH

bull Italy o CRA - Istituto Sperimentale per la Nutrizione delle Piante

bull Sweden o ALCONTROL AB

bull The Netherlands o ALCONTROL BV o Analytico Milieu B V

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

11

13 Summary results and derived performance characteristics The result of the various statistical evaluation including outlier tests calculation of repeatability and reproducibility standard deviation for the congeners of interest can be found in Annex 3 of this report In addition all data submitted by the participants as well as those considered for the calculation of the performance characteristics are listed in Annex 3 to this report Based on these calculations the following results were obtained in the validation round upon statistical evaluation according to ISO 5725-2 The average values the repeatability standard deviation (sr) and the reproducibility standard deviation (sR) were obtained (Table1) The repeatability is determined as an interval around a measurement result (ie repeatability limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by the same laboratory using its own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The repeatability limit was calculated using the relationship r test = f radic2 s rtest with the critical range factor f = 2 The reproducibility like repeatability is also determined as an interval around a measurement result (ie reproducibility limit) This interval corresponds to the maximum difference that can be expected (with a 95 statistical confidence) between one test result and another test result obtained by another laboratory both test results being obtained under the following conditions The tests are performed in accordance with all the requirements of the present standard by two different laboratories using their own facilities and testing laboratory samples obtained from the same primary field sample and prepared under identical procedures The reproducibility limit was calculated using the relationship R = f radic2 sR with the critical range factor f = 2

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

12

Table 1 - Results of the interlaboratory comparison studies of the determination of specific electrical conductivity (EC) in treated biowaste sludge and soil All concentrations are expressed in mSm at 20 deg

Matrix Parameter

Mean sr sR r R p Outliers Total number of data

Number of data reported below detection

Sludge 1 EC 377 143 2850 151 301 14 2 66 0 Sludge 2 EC 436 184 3297 224 402 15 1 67 0 Compost 1 EC 277 179 2566 139 199 14 2 68 0 Compost 2 EC 235 271 3624 178 238 16 0 78 0 Soil 4 EC 103 430 1781 124 512 14 2 62 0 Soil 5 EC 103 600 1615 172 464 13 2 58 0

Abbreviations sr Repeatability standard deviation SR Reproducibility standard deviation r Repeatability limit (comparing two measurements) R Reproducibility limit (comparing two measurements) p Number of labs

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

13

14 Annexes Annex 1 Model questionnaire to be filled by the participating laboratories Annex 2 Report on the validation materials used Annex 3 Statistical calculations Annex 4 Data submitted

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

14

Annex 1

Model questionnaire to be filled by the participating laboratories

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Model questionnaire to be filled by the participating laboratories Name of laboratory Contact person Contact details email Phone Fax Mail address of lab Dispatch address of lab for shipment of samples (no PO boxes) Title of measurement method (copy attached) Our laboratory is willing to participate in the precision experiment for this draft standard method

Yes No As participant we understand that

bull All essential apparatus chemicals and other requirements specified in the method must be available in our laboratory when the programme begins

bull Specified timing requirements such as starting and finishing date of the programme must be rigidly met

bull The method must be strictly adhered to bull Samples must be handled in accordance with instructions bull A qualified operator must perform the measurements

Having studied the method and having made a fair appraisal of our capabilities and facilities we feel that we will be adequately prepared for cooperative testing of this method Comments helliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphelliphellip Signature Date

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

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55L

61L

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Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

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Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

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Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

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Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

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Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

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Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

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Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

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Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

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9L

1L

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Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

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55L

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1L

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Labo

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Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

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Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

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55L

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65L

36L

Labo

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Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

15

Annex 2

Report on the validation materials used

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

VI

Abstract This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

VII

List of Abbreviations Throughout this report the following abbreviations are used

AOX absorbable organic halogens

Corg organic carbon content

Ctotal total carbon content

CAT cation exchangeable

CDD chlorinated dibenzodioxin

CDF chlorinated dibenzofuran

DEHP di(2-ethylhexyl)phthalate

DM dry matter

EPA Environment Protection Agency

EU European Union

FM fresh matter

Hp hepta

Hx hexa

IES Institute for Environment and Sustainability

IRMM Institute for Reference Materials and Measurements

JRC Joint Research Centre

LAS linear alkylsulfonates

LoD limit of detection

LUA Landesumweltamt

Ntotal total nitrogen content

NH4-N Ammonium nitrogen

NO3-N Nitrate nitrogen

NP nonylphenol

NRW North Rhine Westphalia

O octa

P poly

PAH polycyclic aromatic hydrocarbon

PCB polychlorinated biphenyl

Pe penta

T tetra

TEQ toxicity equivalent

UBA Umweltbundesamt

WHO World Health Organization

WWTP waste water treatment plant

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

6

1 Introduction This report gives an overview on the available analytical information on the following raw materials to be used for the production of validation materials of the so-called Project HORIZONTAL

bull Four sludge materials from Duumlsseldorf Germany

bull An agricultural soil material from Reading United Kingdom

bull A compost material from Vienna Austria

bull A compost material from Korschenbroich Germany

bull A sludge-amended agricultural soil from Pavia Province Italy

bull A sludge-amended soil from Barcelona Spain

bull A sludge-amended soil from Essen Germany

bull A long-term sludge exposed soil from Hohenheim Germany

The following analytical information was gathered partly before and during the sampling of the raw materials to be used for the production of the HORIZONTAL validation materials The material were sampled by IES and shipped to IRMM in the course of the year 2005 The information gathered was then completed by various analytical screenings for PAHs and PCBs done by the Institute for Reference Materials and Measurements Geel Belgium for phthalates done by UBA Berlin Germany for PBDE done by IIQAB-CSIC Barcelona Spain for trace elements and some selected major and minor elements by the Institute for Environment and Sustainability Ispra Italy

The work compiled hereafter is based on the numerous additional efforts of the scientists working at various members of the consortium Project HORIZONTAL-Org and contributing organisations

This work is gratefully acknowledged

2 Overview on property values

21 Sludge materials from Duumlsseldorf Germany

The various sewage sludge materials originate from various installations in the North Rhine Westphalia and were produced and sampled by staff from the Landesumweltamt (LUA) NRW under the responsibility from Dr K Furtmann

In total four sludge materials (Sludge A and D from a major municipal WWTP Sludge B from a municipal WWTP with industrial input and Sludge C from a municipal WWTP with high PCB-Content) were obtained and will be blended to two final materials Before sampling the following analytical data for a typical sample were received

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

7

Table 1 ndash Analytical data obtained on an average sludge sample in LUA NRW (with courtesy of K Furtmann LUA Duumlsseldorf)

Parameter Concentration PCB 120 ugkg DEHP 110 mgkg PAH 5 mgkg (EPA) PCDDF 15 ng TEkg PBDE 400 ugkg NP 40 mgkg LAS 3 gkg AOX 300 mgkg

Subsequent screening led to the information displayed hereafter It should be stressed that the data were obtained as SCREENING information on the UNTREATED or partially treated raw materials Therefore the final target values which are relevant for the validation intercomparison can be different

Table 2 ndash Analytical data obtained on a first screening on the sludge samples from LUA NRW

Sewage sludge A

Dusseldorf

sewage sludge D

Dusseldorf PCB (ngg) 28 62 35 52 101 65 101 31 38 118 49 40 153 30 33 105 24 11 138 46 38 156 lt1 lt1 180 34 23 170 23 19 PAH (ngg) Naphtalene 34 381 Acenaphtylene 15 43 Acenaphthene 81 108 Fluorene 94 1167 Phenantrene 3440 Anthracene 22 344 Flouranthene 316 4817 Pyrene 235 3011 Benz(a)anthracene 473 791 Chrysene 691 1078 Benz(b)fluoranthene 538 1688 Benz(k)fluoranthene 228 635 Benz(a)pyrene 383 1114 Indeno(123-cd)pyrene 92 229 Dibenzo(ah)anthracene 71 70 Benzo(ghi)perylene 80 185

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

8

Table 3 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Sludge D (1) 0135 41474 385 Sludge B (2) 0538 0034 30634 547 Sludge A (3) 0184 0037 31399 146 Sludge C (4) 0354 1528 6678 229

Table 4 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Sludge 2

(B)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

554

959

694

591

772

509

nq

nq

970

2216

2379

Table 5 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena IES Ispra Spain) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Sludge 1 (D) 265 290 533 359 1231 338 784 438 lt 005 232 786 Sludge 2 (B) 119 311 626 202 278 299 722 251 lt 005 118 625 Sludge 3 (A) 168 360 621 332 847 416 119 451 lt 005 116 1237 Sludge 4 (C) 563 198 116 273 726 511 473 618 lt 005 444 2015

Table 6 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Sludge 1 (D) 2154 58 844 099 103 101 4367 lt15 50448 Sludge 2 (B) 1067 366 692 046 1491 077 5217 lt15 57633 Sludge 3 (A) 731 663 684 035 1287 068 3733 lt15 60369 Sludge 4 (C) 4379 965 527 163 522 107 5628 lt15 23945

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM)Sludge 1 (D) 03 2403 101 1002 350 15 1944 132Sludge 2 (B) 031 315 97 879 172 12 514 180Sludge 3 (A) 031 1281 153 1567 265 16 1440 168Sludge 4 (C) 055 231 628 2625 371 81 1101 244

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

9

22 Agricultural soil material from Reading United Kingdom

The material was proposed by the University of Reading (S Nortcliff) and was sampled from a site called ldquoFrogmore Farmrdquo which was featured in the ldquoMetalsrdquo Report for HORIZONTAL This site is close to Reading with soils developed on flintyloamy periglacial materials over Chalk has a long and well documented history of sludge application The focus of the work of Nortcliff et al undertook at this site and the monitoring and control at the site (by Thames Water and the subsequent subsidiary bodies dealing with sludge application to soil) was on metals (and metal loads) with no analysis or indeed any form of investigation in to organics in the broadest sense

The analytical information produced in the context of the screening of the raw material is displayed below

Table 7 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 3

(Reading) 0032 0119 669

Table 8 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 9 ndash Analytical data obtained on a first screening on the sludge-amended soil from Reading (courtesy of IRMM)

Parameter Concentration

PCB ngg 28 lt1 52 lt1 101 lt1 118 lt1 153 lt1 105 lt1 138 lt1 156 lt1 180 lt1 170 lt1 PAH ngg Naphtalene lt10 Acenaphtylene 21 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Flouranthene 818 Pyrene 776 Benz(a)anthracene 565

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

10

Parameter Concentration

Chrysene 608 Benz(b)fluoranthene 824 Benz(k)fluoranthene 329 Benz(a)pyrene 799 Indeno(123-cd)pyrene

779

Dibenzo(ah)anthracene 118 Benzo(ghi)perylene 394

Table 10 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 3

(Reading)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

103

003

nq

nq

nq

nd

nd

272

273

Table 11 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 3 (Reading) 015 706 279 138 152 901 267 300 lt 005 258 931

Table 12 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 3 (Reading) 7936 477 112 096 194 017 4107 443 2102 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 3 (Reading) 042 13 45 69 69 69 216 92

Table 13 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 3 (Reading) 012

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

11

23 Compost from Vienna Austria

The fresh compost material was obtained from the Austrian Federal Environment Agency (UBA Vienna) which had used a sub-batch of the raw material for national intercomparson The remainder of the material was stored at 4degC until shipment to IRMM for further processing The following analytical information was provided by UBA Austria and completed with various screenings

Table 14 ndash Analytical data on compost material received from UBA Austria Inorganic and sum parameters

Parameter Unit Sample fraction used Observed mean B CAT mgl FM Fresh sample lt10mm 61 K CAT mgl FM Fresh sample lt10mm 2624 Mg CAT mgl FM Fresh sample lt10mm 242 P CAT mgl FM Fresh sample lt10mm 49 B CAT DM Fresh sample lt10mm 00017 K CAT DM Fresh sample lt10mm 072 Mg CAT DM Fresh sample lt10mm 007 P CAT DM Fresh sample lt10mm 001 NO3-N mgkg FM Fresh sample lt10mm 35 NH4-N mgkg FM Fresh sample lt10mm 230 Ctotal DM lt45degdry milled 29 Corg DM lt45degdry milled 27 Ntotal DM lt45degdry milled 17 P mgkg DM lt45degdry milled 2596 K mgkg DM lt45degdry milled 11019 K DM lt45degdry milled 110 B mgkg DM lt45degdry milled 60 Cd mgkg DM lt45degdry milled 046 Cr mgkg DM lt45degdry milled 25 Cu mgkg DM lt45degdry milled 46 Hg mgkg DM lt45degdry milled 020 Ni mgkg DM lt45degdry milled 18 Pb mgkg DM lt45degdry milled 45 Zn mgkg DM lt45degdry milled 198 Ca mgkg DM lt45degdry milled 68776 Ca DM lt45degdry milled 69 Mo mgkg DM lt45degdry milled 08 S mgkg DM lt45degdry milled 2137 Fe mgkg DM lt45degdry milled 9959 Mn mgkg DM lt45degdry milled 418 Na mgkg DM lt45degdry milled 742 Co mgkg DM lt45degdry milled 41 AOX mgkg DM lt30deg dry milled 62

Table 15 ndash Analytical data on compost material received from UBA Austria Polycyclic aromatic hydrocarbons

PAH Unit Result Naphthaline microgkg DM 93 Acenaphthylene microgkg DM 86 Acenaphthene microgkg DM 5 Fluorene microgkg DM 80 Phenanthrene microgkg DM 89 Anthracene microgkg DM 27 Fluoranthene microgkg DM 487 Pyrene microgkg DM 380

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

12

PAH Unit Result Benzo(a)anthracene microgkg DM 278 Chrysene microgkg DM 317 Benzo(b)fluoranthene microgkg DM 365 Benzo(k)fluoranthene microgkg DM 193 Benz(a)pyrene microgkg DM 320 Indeno(123-cd)pyrene microgkg DM 233 Dibenz(ah)anthracene microgkg DM 67 Benzo(ghi)perylene microgkg DM 225 Sum EPA microgkg DM 3013 Sum EPA mgkg DM 30

Table 16 ndash Analytical data on compost material received from UBA Austria Sum PCDDs and PCBs

Parameter

Dioxine TEQ (ITEF) ngkg DM 73 TEQ (WHO) ngkg DM 35 PCB Σ Ballschmiter mgkg DM 005

Table 17 ndash Analytical data on compost material obtained by screening in IRMM

Parameter Result in ngg

PCB 28 2 52 2 101 4 118 3 153 10 105 1 138 8 156 1 180 5 170 lt1 PAH Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene 26 Fluoranthene 611 Pyrene 510 Benz(a)anthracene 888 Chrysene 957 Benz(b)fluoranthene 1531 Benz(k)fluoranthene 547 Benz(a)pyrene 1101 Indeno(123-cd)pyrene 416 Dibenzo(ah)anthracene 81 Benzo(ghi)perylene 295

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

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ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

13

Table 18 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Compost 1

(Vienna)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

402

019

259

nq

023

004

nq

nq

144

174

259

Table 19 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Compost 1

(Vienna) 0058 1426 557

Table 20 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Compost 1 (Vienna) 039 736 319 410 365 127 495 004 079 013 208

Table 21 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Compost 1 (Vienna) 2063 431 617 426 199 249 1602 lt15 10521

Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Compost 1 (Vienna) 035 3496 81 375 79 55 653 60

Table 22 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Compost 1 (Vienna) 017

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

14

24 Agricultural soil sludge amended soil from Pavia Italy

This sludge-amended soil material was obtained during a monitoring campaign which aimed at a generic description of the over-all soil quality in Pavia Province Italy The material which was collected from the upper horizon originates from a small farm called ldquoCascina Novellordquo During the characterisation of the site the following analytical information was obtained on a pooled sample of a sub-area of the farm of 20 X 20 m2

Table 23 ndash Analytical data on Pavia soil

Parameter Result Al 713 Wgt As 224 mgkg Cd 079 mgkg Cr 59 mgkg Cu 308 mgkg Hg 008 mgkg Ni 344 mgkg Pb 246 mgkg Zn 95 mgkg C 091 Wgt 2378-TCDD 0047 pgg 12378-PeCDD 015 pgg 123478-HxCDD 019 pgg 123678-HxCDD 15 pgg 123789-HxCDD 074 pgg 1234678-HpCDD 26 pgg OCDD 382 pgg 2378-TCDF 068 pgg 12378-PeCDF 053 pgg 23478-PeCDF 071 pgg 123478-HxDF 100 pgg 123678-HxDF 066 pgg 234678-HxDF 16 pgg 123789-HxDF 027 pgg 1234678-HpDF 12 pgg 1234789-HpDF 068 pgg OCDF 33 pgg I-TEQ 20 pgg WHO-TEQ 17 pgg

In addition the screening performed at IRMM did not reveal significant quantities of PCBs and PAHs which were all below the LoDs (1 ngg for PCBs and 10 ngg for PAHs respectively)

Table 24 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 5 (Pavia) 0005 0011 154

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

15

Table 25 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 5

(Pavia)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

039

nq

nq

008

nq

nd

nd

670

671

Table 26 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 5 (Pavia) 033 184 573 225 426 305 206 200 lt 005 381 878

Table 27 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 5 (Pavia) 6939 129 145 224 425 116 6118 255 1789 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 5 (Pavia) 184 62 38 108 55 66 597 110

Table 28 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 5 (Pavia) 006

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

16

25 Sludge-amended-soil from Barcelona Spain

The sludge-amended soil material from Barcelona sampled upon indication from the Barcelorsquo- Group in Barcelona

Table 29 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 2 (Lleida T) 0015 0183 1138

Table 30 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 2

(Lleida T)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

159

045

nq

048

160

nq

nq

1000

1004

Table 31 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 2 (Lleida T) 059 141 327 536 405 186 184 224 lt 005 318 111

Table 32 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 2 (Lleida T) 4443 1067 1429 253 344 204 4116 780 3396 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 2 (Lleida T) 064 65 26 125 59 17 547 65

Table 33 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 2 (Lleida T) 010

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

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ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

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ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

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ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

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Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

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Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

17

26 Sludge amended soil from Essen Germany

The German sludge-amended soil from Essen which was provided as the three sludge materials by LUA NRW did not feature significant concentrations of the PCB congeners 28 52 101 118 153 105 138 156 180 170 but had detectable amounts of some PAHs

Table 34 ndash Analytical screening data on the German sludge-amended soil

Parameter Concentration(ngg)

Naphtalene lt10 Acenaphtylene lt10 Acenaphthene lt10 Fluorene lt10 Phenantrene lt10 Anthracene lt10 Fluoranthene 28 Pyrene 20 Benz(a)anthracene 24 Chrysene 47 Benz(b)fluoranthene 76 Benz(k)fluoranthene 20 Benz(a)pyrene 35 Indeno(123-cd)pyrene 35 Dibenzo(ah)anthracene 10 Benzo(ghi)perylene 26

Table 35 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg dm microgg dm microgg dm microgg dm Wgt Soil 4 (Essen) 0011 0302 055

Table 36 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 4

(Essen)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

nq

nq

nq

nq

nq

nq

128

191

203

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

18

Table 37 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 4 (Essen) 052 545 261 805 320 403 273 273 lt 005 295 781

Table 38 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM) Soil 4 (Essen) 7947 442 085 06 086 007 2163 189 2019 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 4 (Essen) 045 19 42 87 683 60 462 61

Table 39 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 4 (Essen) 004

27 Long-term sludge exposed soil from Hohenheim-Stuttgart Germany

Similarly an additional sludge exposed soil was sampled at the University of Hohenheim Stuttgart were a test soil was long-term exposed to elevated concentrations of sewage sludge

Table 40 ndash Data on phthalate contents (with courtesy of S Heise UBA Germany)

DiBP DBP DCHP DEHP Water microgg TM microgg TM microgg TM microgg TM Wgt Soil 1 (Stuttgart) 0045 0263 1765

Table 41 ndash Data on PDBE contents (with courtesy of D Barceloacute and co-workers IIQAB-CSIC Barcelona Spain)

Soil 1

(Stuttgart)

Tetra-BDE-47

Penta-BDE-100

Penta-BDE-99

Hexa-BDE-154

Hexa-BDE-153

Hepta-BDE-183

Octa-BDE-196

Octa-BDE-197

Octa-BDE-203

Deca-BDE-209

TOTAL

nq

nq

230

006

004

004

nq

nd

nd

498

500

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

19

Table 42 ndash Screening data on some selected trace elements by ICP-AES after micro-wave assisted digestion using aqua regia (with courtesy of F Sena) Note that these data are based on single measurements

Cd Co Cr Cu Mn Ni Pb Sb Tl V Zn μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg μgg Soil 1 (Stuttgart) 069 127 361 262 504 183 252 262 lt 005 266 142

Table 43 ndash Screening data on some selected matrix constituents and elements by WDXRF (with courtesy of S Vaccaro)

Sample SiO2 () Al2O3 () CaO () K2O () Fe2O3 () MgO () TiO2 (PPM) S (PPM) P2O5 (PPM)Soil 1 (Stuttgart) 7194 1006 133 186 366 088 7874 275 3571 Sample Na2O () Cl (PPM) Pb (PPM) Zn (PPM) Cu (PPM) Ni (PPM) Mn (PPM) Cr (PPM) Soil 1 (Stuttgart) 123 50 47 212 85 69 991 129

Table 44 ndash Screening data on mercury by solid-sampling cold-vapour AAS using amalgamation enrichment (with courtesy of G Locoro)

Sample Hg microgg

Soil 1 (Stuttgart) 177

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

rato

ries

Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

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ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

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Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

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Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

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Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

16

Annex 3

Statistical calculations

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

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Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

ries

Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

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Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

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Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

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Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

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Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

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Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

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Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Unit mSm at 20 deg

Mandels k statistics(Compost 1 - EC)Mandels h statistics(Compost 1 - EC)

Sample Compost 1 Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

Element EC

General calcparmT1= 159678E+04T2= 490039E+06T3= 64T4= 348T5= 64446E+02

n= variabelp= 13

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 18933 0032 3 -196 000 Fail 18933 00321 3 2 -2353321L 32517 0087 6 -195 001 Fail 32517 00873 6 5 -233977L 1495667 20142 6 -072 297 Fail - - 7L - - -87664L 1513000 2574 6 -070 038 Fail 1513000 25745 6 5 -859331L 1710000 1581 5 -054 023 Fail 1710000 15811 5 4 -662317L 1800000 - 1 -046 Fail 1800000 - 1 -57231L 2793667 2250 3 037 033 Fail 2793667 22502 3 2 421465L 2958250 9798 4 051 145 Fail - - 65L - - 586034L 2964667 2203 6 051 033 Fail 2964667 22033 6 5 592430L 3105000 4435 4 063 065 Fail 3105000 44347 4 3 732743L 3166500 2660 6 068 039 Fail 3166500 26599 6 5 794226L 3288333 2787 6 078 041 Fail 3288333 27869 6 5 91619L 3325000 3450 6 081 051 Fail 3325000 34496 6 5 952755L 3433333 7711 6 091 114 Fail 3433333 77115 6 5 1061161L 3688333 3920 6 112 058 Fail 3688333 39200 6 5 13161

Totgem 235288 4545 mSm at 20 deg 1-level 232 (176) 13 2372253 (65L7L) 13 12Totstd= 119296 5209 5-level 186 (152) 2

74RESULTS Mean = 23722526mSm at 20 deg

Repeatability variance S2r = 1263638Repeatability std Sr = 355477 --gt 150 r = 99534Between lab variance S2L = 1564693160Reproducibility var S2R = 1565956798Reproducibility std SR = 12513820 --gt 5275 R = 3503869Remarks 2 Labs rejected (65L7L)

000 050 100 150 200 250 300

k-values

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Mandels k statistics(Compost 1 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500

Deviation from Mean

36L

21L

7L

4L

31L

17L

1L

65L

34L

30L

43L

26L

9L

55L

61L

Labo

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Compost 1 - EC -- Mean PARM = 2372 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

7L

31L

1L

34L

43L

9L

61L

Labo

rato

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Mandels h statistics(Compost 1 - EC)

Compost 1-EC

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

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Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

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Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

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Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

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Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

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Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

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Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

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Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Unit mSm at 20 deg

Mandels k statistics(Compost 2 - EC)Mandels h statistics(Compost 2 - EC)

Sample Compost 2 Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

Element EC

General calcparmT1= 172362E+04T2= 478781E+06T3= 78T4= 432T5= 19510E+03

n= variabelp= 16

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 16700 0020 3 -181 000 Fail 16700 00200 3 2 -2051321L 29017 0105 6 -180 002 Fail 29017 01050 6 5 -203904L 1295667 3049 6 -068 056 Fail 1295667 30487 6 5 -772431L 1421667 2927 6 -057 054 Fail 1421667 29269 6 5 -64647L 1440500 3074 6 -055 056 Fail 1440500 30742 6 5 -627570L 1453000 - 1 -054 Fail 1453000 - 1 -615017L 1520000 - 1 -048 Fail 1520000 - 1 -54801L 2182333 2684 3 010 049 Fail 2182333 26839 3 2 114365L 2352750 7575 4 025 139 Fail 2352750 75751 4 3 284734L 2571667 6022 6 044 110 Fail 2571667 60215 6 5 503626L 2745000 8432 6 060 154 Fail 2745000 84321 6 5 67709L 2853333 1966 6 069 036 Fail 2853333 19664 6 5 785343L 2883000 8871 6 072 162 Fail 2883000 88706 6 5 815019L 2908667 6198 6 074 113 Fail 2908667 61976 6 5 840655L 3133333 5203 6 094 095 Fail 3133333 52026 6 5 1065361L 4281667 8377 6 195 153 Fail 4281667 83766 6 5 22136

Totgem 206802 4607 mSm at 20 deg 1-level 233 (176) 16 2068019 () 16 15Totstd= 113375 3042 5-level 186 (152)

78RESULTS Mean = 20680188mSm at 20 deg

Repeatability variance S2r = 3146707Repeatability std Sr = 560955 --gt 271 r = 157067Between lab variance S2L = 1350414435Reproducibility var S2R = 1353561143Reproducibility std SR = 11634265 --gt 5626 R = 3257594Remarks none

000 050 100 150 200

k-values

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Mandels k statistics(Compost 2 - EC)

-2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000 2500

Deviation from Mean

36L

21L

4L

31L

7L

70L

17L

1L

65L

34L

26L

9L

43L

19L

55L

61L

Labo

rato

ries

Compost 2 - EC -- Mean PARM = 2068 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

7L

17L

65L

26L

43L

55L

Labo

rato

ries

Mandels h statistics(Compost 2 - EC)

Compost 2-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Unit mSm at 20 deg

Mandels k statistics(Sludge 1 - EC)Mandels h statistics(Sludge 1 - EC)

Sample Sludge 1 Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

Element EC

General calcparmT1= 219933E+04T2= 907225E+06T3= 66T4= 360T5= 13933E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 32067 0023 3 -196 000 Fail 32067 00231 3 2 -3164221L 49567 0048 6 -195 000 Fail 49567 00480 6 5 -314674L 2210667 5481 6 -063 043 Fail 2210667 54815 6 5 -98567L 2248500 22690 6 -060 178 Fail - - 7L - - -947831L 2511667 5345 6 -044 042 Fail 2511667 53448 6 5 -684670L 2536500 - 1 -043 Fail 2536500 - 1 -659817L 2600000 - 1 -039 Fail 2600000 - 1 -596361L 2718333 7333 6 -032 058 Fail 2718333 73326 6 5 -478065L 3995500 10889 4 046 085 Fail 3995500 108890 4 3 799234L 4267667 3959 6 063 031 Fail 4267667 39591 6 5 1071443L 4410000 3578 6 072 028 Fail 4410000 35777 6 5 1213719L 4779333 6465 6 094 051 Fail 4779333 64646 6 5 1583126L 4781667 37775 6 095 296 Fail - - 26L - - 1585455L 4826667 4033 6 097 032 Fail 4826667 40332 6 5 163049L 4881667 1941 6 101 015 Fail 4881667 19408 6 5 168541L 4928333 3479 3 104 027 Fail 4928333 34790 3 2 17321

Totgem 323613 8074 mSm at 20 deg 1-level 233 (176) 14 3196283 (26L 7L) 14 13Totstd= 163349 10237 5-level 186 (152) 2

78RESULTS Mean = 31962833mSm at 20 deg

Repeatability variance S2r = 2679467Repeatability std Sr = 517636 --gt 162 r = 144938Between lab variance S2L = 2878877519Reproducibility var S2R = 2881556986Reproducibility std SR = 16975149 --gt 5311 R = 4753042Remarks 2 Labs rejected (26L 7L)

000 050 100 150 200 250 300

k-values

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Mandels k statistics(Sludge 1 - EC)

-3500 -3000 -2500 -2000 -1500 -1000 -500 00 500 1000 1500 2000

Deviation from Mean

36L

21L

4L

7L

31L

70L

17L

61L

65L

34L

43L

19L

26L

55L

9L

1L

Labo

rato

ries

Sludge 1 - EC -- Mean PARM = 3196 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

4L

31L

17L

65L

43L

26L

9L

Labo

rato

ries

Mandels h statistics(Sludge 1 - EC)

Sludge 1-EC

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Unit mSm at 20 deg

Mandels k statistics(Sludge 2 - EC)Mandels h statistics(Sludge 2 - EC)

Sample Sludge 2 Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

Element EC

General calcparmT1= 221369E+04T2= 103049E+07T3= 61T4= 317T5= 16848E+03

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

36L 33667 0084 3 -183 001 Fail 33667 00839 3 2 -3548821L 56483 0092 6 -182 001 Fail 56483 00924 6 5 -3526061L 2425000 24656 6 -063 261 Fail - - 61L - - -115754L 2571167 2399 6 -056 025 Fail 2571167 23987 6 5 -1011370L 2698500 - 1 -049 Fail 2698500 - 1 -88407L 2851667 1941 6 -042 021 Fail 2851667 19408 6 5 -730831L 2916667 3502 6 -038 037 Fail 2916667 35024 6 5 -665817L 2960000 - 1 -036 Fail 2960000 - 1 -622565L 3086250 12367 4 -030 131 Fail 3086250 123670 4 3 -496234L 4959667 4694 6 064 050 Fail 4959667 46941 6 5 1377219L 5546500 4738 2 093 050 Fail 5546500 47376 2 1 1964026L 5560000 2236 5 094 024 Fail 5560000 22361 5 4 1977543L 5576667 9688 6 095 103 Fail 5576667 96885 6 5 199429L 5588333 9704 6 096 103 Fail 5588333 97040 6 5 200581L 5749333 3479 3 104 037 Fail 5749333 34790 3 2 2166855L 6348333 14757 6 134 156 Fail - - 55L - - 27658

Totgem 368301 6738 mSm at 20 deg 1-level 233 (176) 14 3582493 (55L61L) 14 13Totstd= 199383 6874 5-level 186 (152) 2

73RESULTS Mean = 35824929mSm at 20 deg

Repeatability variance S2r = 3584704Repeatability std Sr = 598724 --gt 167 r = 167643Between lab variance S2L = 4069455099Reproducibility var S2R = 4073039803Reproducibility std SR = 20181773 --gt 5633 R = 5650897Remarks 2 Labs rejected (55L61L)

000 050 100 150 200 250 300

k-values

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Mandels k statistics(Sludge 2 - EC)

-4000 -3000 -2000 -1000 00 1000 2000 3000

Deviation from Mean

36L

21L

61L

4L

70L

7L

31L

17L

65L

34L

19L

26L

43L

9L

1L

55L

Labo

rato

ries

Sludge 2 - EC -- Mean PARM = 3582 [mSm at 20 deg]

-200 -100 000 100 200

h-values

36L

61L

70L

31L

65L

19L

43L

1L

Labo

rato

ries

Mandels h statistics(Sludge 2 - EC)

Sludge 2-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Unit mSm at 20 deg

Mandels k statistics(Soil 4 - EC)Mandels h statistics(Soil 4 - EC)

Sample Soil 4 Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

Element EC

General calcparmT1= 632135E+02T2= 662727E+03T3= 62T4= 320T5= 94118E+00

n= variabelp= 14

N-table= 5

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -174 Fail 60000 - 1 -4297L 76350 0474 6 -116 047 Fail 76350 04741 6 5 -2654L 86958 0140 6 -079 014 Fail 86958 01398 6 5 -15934L 94050 0077 6 -054 008 94050 00774 6 5 -08826L 96733 0333 6 -044 033 96733 03327 6 5 -06243L 100000 0224 5 -033 022 100000 02236 5 4 -02943L 100000 0224 5 -033 022 100000 02236 5 4 -02931L 105000 0577 4 -015 057 105000 05774 4 3 02155L 105000 0837 6 -015 083 105000 08367 6 5 02119L 106050 0189 6 -011 019 106050 01893 6 5 03270L 113500 - 1 015 113500 - 1 1069L 123333 1751 6 050 174 - - 9L - - 2041L 125000 0141 2 056 014 125000 01414 2 1 22165L 135000 0841 4 091 084 Fail 135000 08406 4 3 32130L 136750 0359 4 098 036 Fail 136750 03594 4 3 33961L 183333 2944 6 262 293 Fail - - 61L - - 804

Totgem 10919 0651 mSm at 20 deg 1-level 233 (176) 14 102885 (61L 9L) 14 13Totstd= 2826 0794 5-level 186 (152) 2

74RESULTS Mean = 1028851mSm at 20 deg

Repeatability variance S2r = 019608Repeatability std Sr = 044281 --gt 430 r = 12399Between lab variance S2L = 316063Reproducibility var S2R = 335670Reproducibility std SR = 183213 --gt 1781 R = 51300Remarks 2 Labs rejected (61L 9L)

000 050 100 150 200 250 300

k-values

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Mandels k statistics(Soil 4 - EC)

-60 -40 -20 00 20 40 60 80 100

Deviation from Mean

17L

7L

4L

34L

26L

43L

43L

31L

55L

19L

70L

9L

1L

65L

30L

61L

Labo

rato

ries

Soil 4 - EC -- Mean PARM = 1029 [mSm at 20 deg]

-200 -100 000 100 200 300

h-values

17L

4L

26L

43L

55L

70L

1L

30L

Labo

rato

ries

Mandels h statistics(Soil 4 - EC)

Soil 4-EC

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Unit mSm at 20 deg

Mandels k statistics(Soil 5 - EC)Mandels h statistics(Soil 5 - EC)

Sample Soil 5 Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

Element EC

General calcparmT1= 595699E+02T2= 624720E+03T3= 58T4= 316T5= 17046E+01

n= variabelp= 13

N-table= 4

Mandels statistics End ResultLAB PARM-gem Stdev N h-mark h k k-markAvX gt AvST+2std AvX lt AvST-2std PARM Stdev Rejlabs N N-1 dev_mean

17L 60000 - 1 -050 Fail 60000 - 1 -4267L 78600 0306 6 -040 029 Fail 78600 03056 6 5 -2404L 88432 0220 6 -035 021 Fail 88432 02197 6 5 -14234L 94783 0294 6 -032 028 Fail 94783 02936 6 5 -07826L 100050 0250 6 -029 024 Fail 100050 02495 6 5 -02531L 103333 0577 3 -027 055 Fail 103333 05774 3 2 00743L 104667 0151 6 -027 014 Fail 104667 01506 6 5 02170L 107000 - 1 -025 Fail 107000 - 1 04455L 111667 0408 6 -023 039 Fail 111667 04082 6 5 0919L 111667 0983 6 -023 093 Fail 111667 09832 6 5 09119L 113800 0730 6 -022 069 Fail 113800 07296 6 5 1121L 127000 - 1 -015 Fail 127000 - 1 24465L 132750 1471 4 -012 139 Fail 132750 14705 4 3 30261L 158333 2563 6 001 243 - - 61L - - 55736L 846667 1531 3 359 145 Fail - - 36L - - 7441

Totgem 15592 0790 mSm at 20 deg 1-level 232 (185) 13 102596 (36L 61L) 13 12Totstd= 19246 0732 5-level 186 (158) 2

67RESULTS Mean = 1025960mSm at 20 deg

Repeatability variance S2r = 037881Repeatability std Sr = 061547 --gt 600 r = 17233Between lab variance S2L = 236771Reproducibility var S2R = 274652Reproducibility std SR = 165726 --gt 1615 R = 46403Remarks 2 Labs rejected (36L 61L)

000 050 100 150 200 250

k-values

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Mandels k statistics(Soil 5 - EC)

-100 00 100 200 300 400 500 600 700 800

Deviation from Mean

17L

7L

4L

34L

26L

31L

43L

70L

55L

9L

19L

1L

65L

61L

36L

Labo

rato

ries

Soil 5 - EC -- Mean PARM = 1026 [mSm at 20 deg]

-100 000 100 200 300 400

h-values

17L

4L

26L

43L

55L

19L

65L

36L

Labo

rato

ries

Mandels h statistics(Soil 5 - EC)

Soil 5-EC

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

17

Annex 4

Raw data submitted

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Sample Compost 1 Sample Compost 1Element EC Element EC

LAB PARM LAB PARM4L 1547 31L 17104L 1512 31L 17204L 1534 31L 17304L 1481 31L 16904L 1487 31L 17004L 1517 9L 3280

65L 2888 9L 333065L 2951 9L 329065L 2895 9L 335065L 3099 9L 333034L 2931 9L 337034L 2992 43L 317734L 2952 43L 318434L 2983 43L 318834L 2970 43L 313134L 2960 43L 31347L 1664 43L 31857L 1693 30L 31207L 1466 30L 31607L 1277 30L 30607L 1237 30L 30807L 1637 17L 1800

21L 3290 70L 167421L 335021L 309021L 325021L 328021L 325055L 348055L 341055L 340055L 353055L 347055L 331026L 325026L 329026L 331026L 326026L 330026L 33201L 27761L 27861L 2819

36L 19336L 18736L 18861L 362061L 371061L 367061L 371061L 373061L 3690

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Sample Compost 2 Sample Compost 2Element EC Element EC

LAB PARM LAB PARM4L 1276 31L 14104L 1295 31L 14404L 1295 31L 14504L 1275 31L 13804L 1355 31L 14004L 1278 31L 1450

65L 2326 9L 286065L 2398 9L 282065L 2259 9L 285065L 2428 9L 288034L 2560 9L 285034L 2534 9L 286034L 2502 43L 281034L 2635 43L 291834L 2544 43L 295434L 2655 43L 27407L 1423 43L 29137L 1412 43L 29637L 1467 19L 28787L 149 19L 29287L 1427 19L 29607L 1424 19L 2798

21L 3030 19L 292821L 2950 19L 296021L 2720 17L 152021L 2940 70L 145321L 286021L 291055L 316055L 322055L 312055L 313055L 307055L 310026L 274026L 280026L 284026L 263026L 266026L 28001L 21521L 21921L 2203

36L 16936L 16736L 16561L 441061L 430061L 428061L 431061L 416061L 4230

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Sample Sewage Sludge 1 Sample Sewage Sludge 1Element EC Element EC

LAB PARM LAB PARM4L 2122 31L 24104L 2195 31L 25404L 2188 31L 25504L 2274 31L 25004L 2256 31L 25204L 2229 31L 2550

65L 3839 9L 488065L 4033 9L 491065L 4019 9L 489065L 4091 9L 489034L 4324 9L 486034L 4277 9L 486034L 4266 43L 436034L 4203 43L 438034L 4282 43L 441034L 4254 43L 44207L 242 43L 44307L 1811 43L 44607L 240 19L 47187L 221 19L 47787L 231 19L 47527L 234 19L 4736

21L 5010 19L 489921L 4970 19L 479321L 4880 17L 260021L 5000 70L 253721L 495021L 493055L 486055L 478055L 485055L 485055L 485055L 466026L 46626L 46626L 46626L 46426L 45926L 4591L 49031L 49141L 4968

36L 32236L 32236L 31861L 277061L 267061L 273061L 268061L 263061L 2830

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Sample Sewage Sludge 2 Sample Sewage Sludge 2Element EC Element EC

LAB PARM LAB PARM4L 2586 31L 29004L 2575 31L 29004L 2532 31L 29504L 2556 31L 28804L 2578 31L 29004L 2600 31L 2970

65L 3050 9L 548065L 3267 9L 548065L 2987 9L 555065L 3041 9L 569034L 5008 9L 566034L 4995 9L 567034L 4984 43L 548034L 4903 43L 567034L 4968 43L 568034L 4900 43L 54507L 283 43L 55607L 285 43L 56207L 283 19L 55137L 288 19L 55807L 286 17L 29607L 286 70L 2699

21L 568021L 569021L 563021L 572021L 570021L 547055L 632055L 654055L 634055L 622055L 650055L 617026L 556026L 557026L 553026L 555026L 559026L 55501L 57241L 57351L 5789

36L 34236L 32736L 34161L 232061L 232061L 241061L 230061L 292061L 2280

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Sample Soil 4 Sample Soil 4Element EC Element EC

LAB PARM LAB PARM4L 86 9L 1504L 86 9L 1304L 89 9L 1204L 88 9L 1304L 86 9L 1004L 87 9L 110

65L 126 43L 9765L 144 43L 10165L 130 43L 10365L 140 43L 9934L 94 43L 10034L 95 19L 10534L 93 19L 10634L 94 19L 10534L 94 19L 10734L 95 19L 1107L 77 19L 1057L 732 30L 1357L 71 30L 1427L 762 30L 1347L 758 30L 1367L 849 17L 60

55L 120 70L 11455L 11055L 10055L 10055L 10055L 10026L 9226L 10026L 10026L 9326L 9826L 981L 126

36L 8936L 87936L 88761L 17061L 18061L 23061L 19061L 14061L 19031L 10031L 11031L 10031L 110

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

Sample Soil 5 Sample Soil 5Element EC Element EC

LAB PARM LAB PARM4L 89 31L 1004L 89 31L 1104L 88 31L 1004L 92 9L 1204L 87 9L 1204L 8573 9L 100

65L 111 9L 10065L 137 9L 12065L 140 9L 1165L 143 43L 10434L 90 43L 10534L 96 43L 10634L 98 43L 10234L 94 43L 10534L 94 43L 10634L 9700 19L 1257L 801 19L 1087L 768 19L 1087L 82 19L 1217L 792 19L 1117L 801 19L 10947L 734 17L 60

55L 110 70L 10755L 11055L 12055L 11055L 11055L 1126L 9926L 10226L 10426L 9726L 9926L 9931L 1271L 124

36L 83536L 86436L 84161L 14061L 12061L 16061L 19061L 18061L 1600

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

European Commission EUR 23013 EN ndash Joint Research Centre ndash Institute for Environment and Sustainability Title Project HORIZONTAL Validation Report on specific electrical conductivity Author(s) E Sobiecka H van der Sloot I Nilsson P Jennische B M Gawlik Luxembourg Office for Official Publications of the European Communities 2007 ndash 54 pp ndash 210 x 297 cm EUR ndash Scientific and Technical Research series ndash ISSN 1018-5593 ISBN 978-92-79-07413-4 Abstract Project HORIZONTAL is interdisciplinary aiming at a harmonisation and horizontal standardisation of test procedures in particular for sludge soils and biowastes In the context of this standardization project a series of draft technical specification were designed upon an extensive desk study fine-tuned after expert consultations and finally validated in international intercomparisons exercise This report summarises the work performed within the validation study of the draft standard for the determination of specific electrical conductivity (EC) in soils sludge and treated bio-waste using gravimetric method It further explains the underlying statistical concept for the calculation of reproducibility and repeatability from intercomparisons data In addition all single values results of the statistical evaluation as well as background information on the validation materials used are described and explained

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C

The mission of the JRC is to provide customer-driven scientific and technical support for the conception development implementation and monitoring of EU policies As a service of the European Commission the JRC functions as a reference centre of science and technology for the Union Close to the policy-making process it serves the common interest of the Member States while being independent of special interests whether private or national

LB

-NA

-23013-EN

-C