Results of the 20th and 21st Needle/LeafResults of the 20th and 21st Needle/Leaf Interlaboratory Comparison Tests

Alfred FÜRST

Brussels/Belgium 27.03.2019

ICP-FORESTS - Combined Expert Panel Meeting

Overview

G l i f ti b t b th t tGeneral information about both testsCommon methodsSelected resultsProblematic parameters / laboratories which failed in both testsRe-qualification after 20th and 21st testReference samples for method validationReference samples for method validationMeasures for checking data quality (control charts, ring tests)Ongoing foliage ringtest program 2019/2020Urgent request for new ringtest sample material!Urgent request for new ringtest sample material!

Needle/Leaf Interlaboratory Comparison tests

Countries/Laboratories(Level II - foliage samping in uneven years)

Test Year Number of countries

Number of laboratories

10th

2007/08 29 54

( g p g y )

11th

2008/09 28 56

12th

2009/10 30 56

13th

2010/11 29 60th

14th

2011/12 28 62

15th

2012/13 28 61

16th

2013/14 25 57

17th

2014/15 25 5417 2014/15 25 54

18th

2015/16 25 53

19th

2016/17 22 45

20th

2017/18 23 4820 2017/18 23 48

21st

2018/19 24 52

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Difficult Samples & Concentrations

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Evaluation procedure Non-tolerable results76 sample/parameter combinations per test

20%

]

resultsp p p

s [8

0-12

le L

imits

Target value: Outlier free mean [51.77 ng/g] Tole

rabl

g [ g g] T

Max. acceptable limit of quantification [10 ng/g]+

Percentage of non-tolerable results

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Pre-treatment methods 2018/19

Elementanalyzer

Elementanalyzer

Elementanalyzer

Elementanalyzer

Determination methods 2018/19

Kjeldahl

Photometry

Pre-treatment / Determination methods

1 Microwave digestion ICP AES or ICP MS1. Microwave digestion – ICP-AES or ICP-MS

2. Pressure digestion – ICP-AES or ICP-MS

3 N t t t El t l (C N S H )3. No pretreatment – Element analyzer (C, N, S, Hg)

4. Open digestion – Flame-AAS

5. Open digestion – Kjeldahl (N), Phosphorous (UV/VIS)

6. No pretreatment – X-Ray methods

Comparison between 12th and 21st TestElement 12

thInterlaboratory Comparison Test 2009/10 

(Sample 3) ‐ Bears garlic 

21stInterlaboratory Comparison Test 2018/19 

(Sample 1) ‐ Bears garlic (Unit) Mean Participating labs Mean Participating labs

N 49.64 49.85mg/g 53 45

S 11.66 11.30mg/g 50 43 

P 3.80 3.85/ 53 46mg/g 53 46

Ca 5.86 5.81mg/g 54 46

Mg 2.20 2.18mg/g 54 47g/g

K 25.16 25.63mg/g 54 47

C 47.73 48.21g/100g 47 42

Zn 31.84 31.47μg/g 43 38

Mn 56.15 55.93μg/g 44 39

Comparison between 12th and 21st TestElement 12

thInterlaboratory Comparison Test 2009/10 

(Sample 3) ‐ Bears garlic 

21stInterlaboratory Comparison Test 2018/19 

(Sample 1) ‐ Bears garlic (Unit) Mean Participating labs Mean Participating labs

Fe 144.57 141.75μg/g 42 35

Cu 9.11 9.11μg/g 40 37

Pb 0.28 0.25/ 30 28μg/g 30 28

Cd 61.22 66.11ng/g 28 29

B 17.03 16.92μg/g 23 23μg/g 3 3

As 30.40 36.81ng/g 2 14

Cr 1.06 1.05μg/g 10 23

Co 0.049 0.046μg/g 7 21

Hg 8.06 7.62ng/g 7 16 +

Parameters / Participating labs

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New Parameters / Participating labs

NitrogenTest non tolerable results [%]

15th Test 6.016th Test 3 116th Test 3.117th Test 2.118th Test 7.919th Test 4.620th Test 3.721 t T t 16 121st Test 16.1

Nitrogen results in the 21st Test

Method passed failed % failedDA01: N analyzer >100mg 64 12 15 8

Sample results

DA01: N analyzer >100mg  64 12 15.8DA02: N analyzer <100mg + extra milling 46 6 11.5DZ02: Kjeldahl method 21 11 34.4DA99: Other Element analyzer method 4 ‐ 0%DB01: AAS‐flame technique (C2H2/Air) 4 ‐ 0%DB08: ICP‐AES without Ultrasonic  4 ‐ 0%nebulisationDF08: Other Potentiometric titration 4 ‐ 0%DZ99: Detection method not in this list 4 ‐ 0%DZ99: Detection method not in this list 4 0%

Nitrogen (Kjeldahl method)

Laboratories: A43, A88 an S22

Methodical problems!

o Digestion not complete (which catalyst?)o Contaminationo …….o Wrong units (A88)

Method validation with different types ofMethod validation with different types ofreference materials

Nitrogen (element analyzer)

Laboratories: A56, A57, A59, abo a o es 56, 5 , 59,A62 and A85

Calibration error!

Method validation with reference material

SulphurTest non tolerable results [%]15th 13.916th 14 816th 14.817th 9.918th 6.419th 7.420th 16.721st 16 921st 16.9

Sulphur results in the 21st Testh d d f l d f l dMethod passed failed % failed 

DA01: Macro Elemental‐analyzers for C, N or S for solids (Sample > 100mg)

27 9 25.0( p g)

DA02: Macro Elemental‐analyzers for C, N or S for solids (Sample < 100mg)&milling step

3 1 25.0

DA99: Other Element analyzer method 3 1 25 0DA99: Other Element analyzer method 3 1 25.0

DB08: ICP‐AES without Ultrasonic nebulisation 89 7 7.3

DB09: ICP‐AES with Ultrasonic nebulisation 4 ‐ 0.0

DB10: ICP‐MS 6 6 50.0

DB99: Other Atomic Absorption or Emission Spectroscopy method

2 2 50.0p pyDD02: X‐ray methods 7 1 31.3

DE01: UV‐VIS‐spectrophotometry‐technique 2 2 50.0

Relative abundance of Sulphur and possible interferences in ICP MSpossible interferences in ICP–MS

R l tiIsotope

Relative abundance (%) m/z Possible interferences

32S 95.018 32 16O2, 14N18O, 15N17O, 31P1H33S 0.760 33 16O17O, 32S1H34S 4.215 34 17O2, 16O18O, 33S1H36S 0.014 36 18O2, 35Cl1H, 36Ar

Sulphur with ICP-MS

Problematic element for ICP-MS

Diatomic interferences with N, O and Ar on prominent isotope

masses

“Best” is to determine 32S16O on mass 48 in an oxidizing plasma

Special equipment like collision cells and reactive gases are Spec a equ p e t e co s o ce s a d eact e gases a e

useful

Best solution is to change the method (ICP-AES) Best solution is to change the method (ICP-AES)

Calcium in the 21st Test

Method passed failed  % failed 

fl h i ( / i )

Sample results

DB01: AAS‐flame technique (C2H2/Air) 12 8 40.0

DB02: AAS‐flame technique (C2H2/N2O) 4 ‐ 0.0

DB08: ICP‐AES without Ultrasonic nebulisation 108 8 6.9DB08: ICP AES without Ultrasonic nebulisation 108 8 6.9

DB09: ICP‐AES with Ultrasonic nebulisation 5 3 37.5

DB10: ICP‐MS 11 5 31.3

DD01/DD02: X‐ray methods 11 5 31.3

DA01:Macro Elemental‐analyzers for C, N or S for solids (Sample > 100mg)

4 ‐ 0.0for solids (Sample  > 100mg)

Calcium

DB01: AAS‐flame technique (C2H2/Air): o Buffer against P & Si interferences (La or EDTA)o Buffer against P & Si interferences (La, or EDTA)

o Matrix adapted Standards (especially the acid mixture & concentration)

DB09 & DB10: ICP‐AES with Ultrasonic nebulisation & ICP‐DB09 & DB10: ICP‐AES with Ultrasonic nebulisation & ICP‐MS – too sensitive!

Best choice: DB08: ICP‐AES without Ultrasonic nebulisation

Arsenic Percentage ofnon tolerable

res ltsresults

Higher Concentrations better resultsLabs with too high LOQ failed

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Arsenic results in the 21st Test

Method passed failed  % failed

DB08: ICP AES without Ultrasonic nebulisation 2 10 83 3

Sample results

DB08: ICP‐AES without Ultrasonic nebulisation 2 10 83.3

DB10: ICP‐MS 38 2 5.0

DB99: Other Atomic Absorption or Emission 4 0 0DB99: Other Atomic Absorption or Emission Spectroscopy method

4 ‐ 0.0

Only the ICP-MS method is recommended

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Mercury Percentage ofnon tolerable

res ltsresults

Really good results!

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Mercury results in the 21st Test

Method passed failed  % failed

DA05: Hg Analyzer 27 0 0

Sample results

DA05: Hg‐Analyzer 27 ‐ 0.0

DB03: AAS‐cold vapor technique 4 2 33.3

DB04: AAS hydride technique 2 1 33 3DB04: AAS‐hydride technique 2 1 33.3

DB08: ICP‐AES without Ultrasonic nebulisation 3 ‐ 0.0

DB10 ICP MS 9 0 0DB10: ICP‐MS 9 ‐ 0.0

Really good results!

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With different methods (Mercury analyzer, AAS hydride, AAS cold vapor, ICP-MS, ICP-AES)!

Low concentrations

Changes in the ranking of these „bad“ labsfrom the 20th to the 21st testfrom the 20 to the 21 test

F21 F09 A45A43A88F24F24A56A62

ICP-Forests laboratory

Reasons for Re-Qualificationafter the 20th Needle/Leaf Ringtestafter the 20th Needle/Leaf Ringtest

1 T h i l bl (4 l b )1. Technical problem (4 labs)2. Methodical problem / method changed (4 labs)3. Calibration error (2 labs)4. Contamination (2 labs)5. LOQ “adjusted”? (2 labs)6. Missed data submission deadline or got no samples (one lab)6. Missed data submission deadline or got no samples (one lab)7. Transcription error (one lab)8. Fault of a labworker (one lab)9 No error found (one lab)9. No error found (one lab)

Labs failed with the same element/s in both testsin both testsRussia - A39 (As),

Germany - A56 (C),

Denmark - A60 (S)Denmark A60 (S),

Croatia - A62 (Ca),

Germany - A82 (K),

Germany - F07 (As, Cr), y ( , ),

Hungary - F21 (Ca) ICP-Forests laboratory

What happend in former tests?

Ring test N S P Ca Mg K Cg g

17th Test <>> < <

18th Test < <<<> <>> <<> <>>

19th Test > <<<< >>>> <<<

20th Test < <> <<<< <<< <<<

21st Test << >>>> <<<< < < <

M i t thi i f t ???Measures against this error in future ???

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QA/QC Manual

When a (ICP-Forests) lab did not qualify and did not make efforts e a ( C o es s) ab d d o qua y a d d d o a e e o sto requalify, the ring test organizers [ICP Forests PCC] will send a letter to the National Focal Centre and inform them about the consequence that their data possibly cannot be used forconsequence that their data possibly cannot be used for evaluations on an European level.

Th lt f th i t t i t t d i th d t b f thThe results of the ring tests are integrated in the database of the PCC. This means that the bad ring test results will be marked as disqualified and this information can be used as a selection criterion for the monitoring data used in evaluations.

Re-qualification process

Please, ask your colleagues, if they have similar problems!Please, ask me for help with reference material or for hints.

Re-Qualification after the21st Needle/Leaf Ring Test21st Needle/Leaf Ring Test

Is mandatory for all „ICP-Forests laboratories“ if theyplan to:

Submit monitoring results from the sampling period2018/19 to the PCC database („growing saison“ 2018)2018)

Re-qualification process

Is a hard work for you (as headf th l b) i l b tof the lab) in your laboratory

and it needs time and it needsand it needs time and it needsmoney!

Re-qualification process

Final Deadline for finishing the requalification is 1st of September 2019

Yo r report has to contain o r labcode andYour report has to contain – your labcode and:

• Results of the re-analyzed ring test samples.P i t t f th i t t ( lib ti lib ti f t• Printouts from the instruments (calibration curves, calibration factors, measured results, date/time)

• Sample weights, dilution factors, moisture correction factors (if needed)Statement of the reason for failing the qualification• Statement of the reason for failing the qualification

• Measures against this error in future• Deadline for submitting your first draft report is 1st of August 2019!

This deadline is needed to discuss open questions in time before theThis deadline is needed to discuss open questions in time before the final deadline.

Special helping offer for these fourICP Forests labs (A60 A62 F07 F21)ICP-Forests labs (A60, A62, F07, F21) which failed in both testsRe-qualification (as usal)

Hint for avaliable reference materials (www.ffcc.at) for method validationFour extra unknown samples from older ring tests to check the measures in the lab before the next ring test!

A re-qualification is then only possible with all needed documents andcorrect results of these four extra samples!

At the moment two labs F07 and A62 haveAt the moment two labs F07 and A62 have requested these samples!

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Reference material for methodvalidationvalidation

Maple leaves A• Maple leaves A• Litterfall-beech leaves (included As, Cr, Co, Hg, Ni)• Pine needles (Pinus nigra)

Spr ce needles B (incl ded As Cr Co Hg Ni)• Spruce needles B (included As, Cr, Co, Hg, Ni)

Details: http://bfw.ac.at/rz/bfwcms2.web?dok=5146

Accreditation status according EN 17025EN 17025

Types of control charts used in foliar laboratories (90 2% are using it !?)laboratories (90.2% are using it...!?)

Each ICP-Forests lab had to use it!

Normal analytical run in the lab

Calibration OK Samples OK

Control Chart (Average chart) –Internal Quality ControlInternal Quality Control

Results of these QC samples over time

Normal analytical run in the lab

These labs use control charts foranalyzing the four test samples !?analyzing the four test samples…!?

Labcode N S P Ca Mg K CA62 < <> <<<< <<< <<<

Labcode N S P Ca Mg K C

A85 >>> <<< <<<< <<<< <<<< <<<< >>>>

< too low result< too low result> too high result

What is a good result?

% Recovery close to 100% with a small variation between the foursample results and without influence of the sample concentration(= your method is under control)

Vi (variation between the four replicates)o element analyzer (measurement without extra sample preparation) < 3%o Macro elements (P, K, Ca, Mg, K) < 5%o Micro elements and heavy metals < 10%o Trace elements < 20%

Accuracy of the mean & precision

% R 97 79 99 93% Vi 0 60 1 17%% Recovery = 97.79 – 99.93% Vi = 0.60-1.17%

% Recovery = 86.22 – 131.2% Vi = 2.97-7.89%

Frequency of ring test participation/year

22nd Needle/Leaf InterlaboratoryComparison Test 2019/20Comparison Test 2019/20

http://bfw.ac.at/ws/ring_nadel.login

Timetable - 22nd Test

Informing the participating labs via email (Febuary 2019)o g e pa c pa g abs a e a ( ebua y 0 9)• Registration of the participants via internet (Deadline July 1st,

2019) • Distribution of four test samples with an invoice (July 2019)• Distribution of four test samples with an invoice (July 2019) • Data submission by the labs (October-December 2019)• Deadline of data submission (Deadline January 1st, 2020)

Fi t lt (J 2020) d lifi ti t t d• First results (January 2020) and re-qualification process started• Final Report and online qualification report (February 2020)• Re-qualification process finished (Deadline September 1st, q p ( p

2020)

Samples for one of the next tests

6 of the last 8 foliage/litterfall samples are prepared from6 o e as 8 o age/ e a sa p es a e p epa ed oAustria

A lot of the samples have a low concentration of heavy metals A lot of the samples have a low concentration of heavy metals(Cd, Pb, As, Co, Hg)

I need someone who is willing to collect a sample!Leaf samples (beech?) are highly welcome!Heavy metal polluted samples are especially needed!

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