analytische qualitätssicherung baden-württemberg · relative standard deviation and tolerance...

Analytische Qualitätssicherung

Baden-Württemberg

PT-WFD

Proficiency Test 5/11 Priority pesticides in surface water

aclonifen, alachlor, atrazine, bifenox, chlorfenvinphos,

chlorpyrifos, cybutryne, diuron, isoproturon, quinoxyfen, simazine, terbutryn, trifluralin

provided by

AQS Baden-Württemberg at Institute for Sanitary Engineering, Water Quality and Solid Waste Management,

University of Stuttgart Bandtäle 2, 70569 Stuttgart-Büsnau, Germany

in cooperation with other European PT providers

Stuttgart, in December 2011

Responsibilities: Scientific director AQS: Dr.-Ing. Dipl.-Chem. Michael Koch PT manager: Dr.-Ing. Frank Baumeister AQS Baden-Württemberg at Institute of Sanitary Engineering, Water Quality and Solid Waste Management at University of Stuttgart Bandtäle 2 70569 Stuttgart-Büsnau Germany http://www.aqsbw.de Tel.: +49 (0)711 / 685-65446 Fax: +49 (0)711 / 685-63769 E-Mail: [email protected]

PT-WFD – priority pesticides page 1 INDEX OF CONTENTS

1. GENERAL ........................................... ............................................................. 3

2. PT DESIGN ...................................................................................................... 4

3. SAMPLE PREPARATION ................................ ................................................ 4

4. SAMPLE DISTRIBUTION ............................... ................................................. 4

5. ANALYTICAL METHODS ................................ ................................................ 5

6. SUBMISSION OF RESULTS ............................. .............................................. 5

7. EVALUATION AND ASSESSMENT ......................... ....................................... 5

8. PARTICIPATION ..................................... ......................................................... 5

9. EXPLANATION OF APPENDIX A ......................... .......................................... 6

10. EXPLANATION OF APPENDIX B ......................... .......................................... 8

11. EXPLANATION OF APPENDIX C ......................... .......................................... 8

12. MEASUREMENT UNCERTAINTY ........................... ........................................ 9

13. TRACEABLE REFERENCE VALUES ........................ ................................... 10

14. INTERNET ...................................................................................................... 12

Appendix A ACLONIFEN ......................................... .......................................................... A-1 ALACHLOR ........................................ ........................................................... A-7

ATRAZINE ......................................... ........................................................... A-14

BIFENOX ...................................................................................................... A-21

CHLORFENVINPHOS .................................................................................. A-28

CHLORPYRIFOSETHYL ................................ .............................................. A-35

DIURON ........................................................................................................ A-42

ISOPROTURON ........................................................................................... A-49

QUINOXYFEN .............................................................................................. A-56

SIMAZINE ..................................................................................................... A-63

TERBUTRYN ................................................................................................ A-70

TRIFLURALIN ...................................... ........................................................ A-77

CYBUTRYNE ................................................................................................ A-83

Appendix B

PT-WFD – priority pesticides page 2 Appendix C ACLONIFEN ......................................... .......................................................... C-1 ALACHLOR ........................................ ......................................................... C-10

ATRAZINE ......................................... ........................................................... C-19

BIFENOX ...................................................................................................... C-28

CHLORFENVINPHOS .................................................................................. C-37

CHLORPYRIFOSETHYL ................................ .............................................. C-46

DIURON ........................................................................................................ C-55

ISOPROTURON ............................................................................................ C-64

QUINOXYFEN ............................................................................................... C-73

SIMAZINE ..................................................................................................... C-82

TERBUTRYN ................................................................................................ C-91

TRIFLURALIN ...................................... ....................................................... C-100

CYBUTRYNE .............................................................................................. C-109

PT-WFD – priority pesticides page 3

1. General This PT was provided by AQS Baden-Württemberg in the context of the “PT-WFD” network of European PT providers for the determination of:

• aclonifen • alachlor • atrazine • bifenox • chlorfenvinphos • chlorpyrifos (chlorpyrifos-Ethyl) • cybutryne • diuron • isoproturon • quinoxyfen • simazine • terbutryn • trifluralin

The PT met the requirements of the water framework directive and the related envi-ronmental quality standards for the determination of priority substances in surface water. More information about this network can be found on the webpage http://www.pt-wfd.eu. The PT was organized in collaboration with the following other PT providers in Eu-rope: Kemijski inštitut Ljubljana Slovenija, SI-1001 Ljubljana, Hajdrihova 19, p.p.660, Tel.: 01/476 02 00, Faks: 01/476 03 00, mail: [email protected] QualityConsult , Via G. Bettolo 4, (00195) Rome Italy, Tel.: +39 320-6905464, Fax: +39 0697840718, [email protected] VITUKI Nonprofit Ltd. , Quality Assurance and Control, 1095 Budapest, Kvassay J. 1., HUNGARY, Tel: +36 1 215-6140/ext. 2199, Fax: +36 1 215-6046, [email protected] Proftest SYKE Finnish Environment Institute , Laboratories, Hakuninmaantie 6, FI 004300 Helsinki, FINLAND, Tel: +358 20 610 123, Fax: +358 9 448 320, [email protected] The PT was executed and evaluated due to the requirements of the PT-WFD net-work.


2. PT design Each participant received the following samples:

- 3 x 2 samples for the determination of the mentioned parameters in 1000–ml-glass bottles, screw capped with PTFE sealing. The samples were stabilised by cooling.

3 different concentration levels/batches were produced. All participants received the same concentration levels.

3. Sample preparation The samples were based on a real surface water. The surface water was filtered by using 5 µm cartridges to eliminate course particles. To reduce germs, the surface water was irradiated with ultraviolet light. For preparation of the samples, the surface water was spiked with a solution of the substances dissolved in DMF. The concentrations of the analytes of the spiked samples was based on the analyti-cal feasibility and on the values of article 4 of the commission directive 2009/90/EC of the European communities for the technical specifications for chemical analysis and monitoring of water status in the context of the water framework directive. According to the Environmental Quality Standard (Directive 2008/105/EG on envi-ronmental quality standards in the field of water policy), the AA-EQS values are as follows: Parameter (proposed) AA -EQS [µg/l] aclonifen (0,120) alachlor 0,3 atrazine 0,6 bifenox (0,0125) chlorfenvinphos 0,1 chlorpyrifos (chlorpyrifos-Ethyl) 0,03 cybutryne (0,0016) diuron (0,15) isoproturon 1 quinoxyfen (0,065) simazine 0,03 terbutryn (0,120) trifluralin 0,3 AA: annual average The samples were cooled directly after preparation and dispatched with freezer packs added to the packages.

4. Sample distribution The samples were dispatched on 25th October 2011 by express service. Laboratories registered at one of the cooperating PT providers received the samples from there. The participants were informed to store the samples under cooled conditions directly after receipt and to start with the analysis of the samples as soon as possible, but one day after receipt at the latest.


5. Analytical methods The participants were free to choose a suitable method, but a maximum limit of quan-tification (LOQ) for all parameters of 0,025 µg/l was required. According to the “Tech-nical Agreement” of the PT-WFD network, the limit should correspond to 30% of the environmental standards of the directive 2008/105/EG on environmental quality standards in the field of water policy. Since the directive requirements in this case are not always achievable, the LOQ was chosen due to common practice (see also chap-ter “sample preparation”). The samples had to be analysed in duplicate over the complete method (sample preparation and measurement). The participants were asked to submit the results as average values in µg/l with four significant digits.

6. Submission of results The deadline for the submission of results was on 14th November 2011.

7. Evaluation and assessment According to the agreements in the PT-WFD network the following procedure was used for the evaluation and assessment of the PT round: The reference values (see chapter “Traceable reference values”) were used as assigned value X. A fixed value of 25% of the assigned value was used as standard deviation for profi-ciency assessmentσ) . For each measurement result of the participant a z-score was calculated using the following formula:

σ)Xx

z−=

for the assessment the following criteria were used: |z| ≤ 2,0 satisfactory 2,0 < |z| < 3,0 questionable |z| ≥ 3,0 unsatisfactory

8. Participation Number of participants (total): 33 Registration via: AQS Baden-Württemberg, Germany: 29 Kemijski inštitut, Slowenien: 0 QualityConsult, Italien: 2 VITUKI, Ungarn: 1 SYKE, Finland: 1 Figure 1 shows the percentage of satisfactory, questionable, unsatisfactory results and not submitted results.


Figure 1: Percentage of satisfactory, questionable, unsatisfactory and not submitted results.

9. Explanation of Appendix A Appendix A contains for each parameter

• parameter tables • a figure of participants’ means (calculated with Algorithm A) versus the spiked

amounts for the determination of the recovery rate and the matrix content • a figure of the relative standard deviations versus the concentrations • a figure of the tolerance limits in the PT versus the concentrations • the frequency of application of analytical methods • the method specific evaluation • a comparison of mean and reference values for each concentration level • a comparison of the relative standard deviations of the different methods • the statistical characteristics of the method specific evaluation • a tabular comparison of the means with the reference values and their uncer-

tainties Parameter tables

In these tables the following values for each concentration level are listed:

• assigned value • expanded uncertainty of the assigned value in % (see chapter “Traceable ref-

erence values”) • standard deviation, calculated using robust statistical method (Algorithm A) • standard deviation for proficiency assessment in µg/l for the calculation of z-

scores (25 % of the assigned value) • rel. standard deviation for proficiency assessment in % • tolerance limits above and below in µg/l and % • number of values in this level

64

8489

67 7265

82 85

53

85 83

61 65

13

3121 22

15 12

36

9

30 27

55

6

34

4322

1

64

2

55

9

5

82

2

2

21

1 432

3 3

0%

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100%

aclon

ifen

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frequ

ency

in% no participation

unsatisfactory

questionable

satisfactory


• number of not satisfactory values below and above the assigned value and the percentage of these values in total.

Determination of recovery rate

In the diagrams of the mean values versus the spiked amount of analyte a linear re-gression line was calculated using a generalized least square regression which takes into account the uncertainties of the values in both directions. From this regression line the recovery rate for each parameter was determined (see diagrams). The slope of the line indicates the average recovery rate and the x-axis intercept corresponds to the matrix content. Since in the present case the surface water used was not ex-pected to contain the pesticides to be analysed and the uncertainty of the matrix con-tent calculation from the diagrams were always higher than the value itself, it was decided to not use any matrix content for the calculation of reference values for this PT round. The diagrams also contain the expanded uncertainty (k=2) of the spiked amount and the mean values. Figure 2 gives an overview of all average recovery rates for all parameters.

Figure 2: Average recovery rates for all parameters For most of the parameters the average recoveries are significantly below 100%, es-pecially for bifenox and trifluralin, where the recoveries are quite low. Relative standard deviation and tolerance limit

The diagrams for the rel. standard deviation vs. the assigned value show the values compared to the fixed standard deviation for proficiency assessment (horizontal line at 25%) and the concentration dependence. The diagrams with the tolerance limits show the limits in percent.

91,6100,1

90,5

75,5

100,7 100,294,1 95 93,4 91,1

96,987,8

97,4

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PT-WFD – priority pesticides page 8 Method specific evaluation

For each parameter the methods used by the participants are shown in a diagram. In a second diagram for each method values are sorted in 5 categories: too low results with z-score < -2 low results with –2 ≤ z-score < –1 correct results with –1 ≤ z-score ≤ +1 high results with +1 < z-score ≤ +2 too high results with z-score > +2 Comparison of means and reference values for each c oncentration level

Finally the mean value calculated from all results (Algorithm A) and the reference value are compared with mean values calculated for all methods separately (in this case using the Hampel estimator described in ISO/TS 20612). Mean values were calculated only, if more than 7 results were within a z-score-range of ± 2. The means are reported with their expanded uncertainty calculated according to ISO 13528.

10. Explanation of Appendix B Participants were asked to report expanded uncertainties of their results on a volun-tary basis. In this diagram for each parameter the reported uncertainties for all con-centration levels with the reproducibility standard deviation (horizontal line) are dis-played. Values which deviate from the reproducibility standard deviation with a factor more than 2 are usually not realistic.

11. Explanation of Appendix C In the last part of the report, for all concentration levels the results of all participants are illustrated. Confidentiality of participants is ensured by using lab codes. The lab codes were sent to participants with the certificates. In detail Appendix C contains:

• a table with all data • figures with

o all reported results o all z-scores o all reported expanded uncertainties o all ζ−scores

Table with all data

The assigned value with the expanded uncertainty and the tolerance limits for the concentration level is illustrated in the table. For each participant the following data are given:

• lab code • reported result • measurement uncertainty of the value (if reported) • ζ-score for this value, calculated with the following formula

22reflab uu

xx

+

−=ζ , with

xx − = difference from the measured value and the assigned value ulab = standard uncertainty of the value, reported by the participant uref = standard uncertainty of the assigned value

• z-score for proficiency assessment


• assessment of the value according to its z-score o s: satisfactory o q: questionable o u: unsatisfactory

Meaning of ζ-scores: The assessment of ζ-scores is similar to that of z-scores. If the data are normally dis-tributed and the uncertainties are well estimated, ζ-scores will lie between -2 and +2 with a probability of around 95 %. ζ-scores are mainly influenced by the measurement uncertainties reported by the laboratory. Therefore ζ-scores are usually not appropriate for the assessment of the reported results, unless the reported measurement uncertainty is checked for fitness-for-purpose. Therefore we do not use the ζ-scores for the assessment of the laboratories. Nevertheless ζ-scores are appropriate to check the plausibility of the reported meas-urement uncertainty: If the z-score of a result is within the tolerance limit and the ζ-score is outside, then the measurement uncertainty is underestimated. If the z-score is outside the tolerance limits and the absolute value of the ζ-score is lower than two, then the requirements of the proficiency test were stronger compared with the reported measurement uncertainty. Diagrams of uncertainty data In the first figure for all lab codes the measurement uncertainty (together with the re-producibility standard deviation) is illustrated. The second figure shows the associat-ed ζ-scores.

12. Measurement uncertainty 13 (40,6%) out of 32 laboratories with valid values reported measurement uncertain-ties. In total 382 (36,9%) out of 1034 valid values were given with the measurement uncertainty. The following table displays the number of values with measurement uncertainty against the accreditation status.

Accreditation status of the values

Number of values

Number of values with meas-urement uncertainty

accredited 549 291 (53,0%) not accredited 200 55 (27,5 %) not specified 285 36 (12,6 %)

We would like to put emphasis on the fact that reporting of measurement uncertain-ties in our PT scheme is absolutely voluntary. The only objective is to help all partici-pants to reasonably handle measurement uncertainties and their estimation. The diagrams show that the spread of reported uncertainties in some cases is vast, in many cases unrealisticly low values were reported. A plausibility check using re-producibility standard deviations of the PT round could be helpful here. If measurement uncertainties are underestimated values assessed as “satisfactory” in the PT (|z| ≤ 2), will have a large ζ-score. |ζ| > 2 means that the “own” require-ments (defined in terms of estimated uncertainty) are not fulfilled. 124 (35,7%) out of the 347 values reported with uncertainties and having a z-score |z| ≤ 2.0 had a ζ-score > 2.0. This means that the requirements of the PT scheme have been fulfilled , but not the “own” requirements, the uncertainty is underestimat-ed.


13. Traceable reference values Traceability of analytical results to national and international references is of increas-ing importance in all laboratories. This is not easy to realise for chemical analyses and often can only be done by analysing certified reference materials. But availability of these reference materials in the water sector is very limited. Therefore we try to provide reference values for the proficiency test samples, traceable to national and international references. Since our PT samples without exception are spiked, real water samples, reference values can be calculated from the sum of matrix content and spiked amount of ana-lyte. For both summands traceable values and their uncertainty have to be deter-mined. Thereby we assume that no unrecognised bias resulting from sample prepa-ration and transport is present and that we recognise all uncertainty components. Determination of the spiked amount and its uncertai nty

All spiking of samples was controlled gravimetrically. Conversion to concentration was done by measuring the density of the resulting samples using a pycnometer. This procedure allows the preparation of a complete uncertainty budget. The first step is the specification of the measurand with a formula. This shows the links between the result and all influence quantities:

with: clot concentration of the analyte in the lot resulting from the spike in g/l msubst_ss mass of the standard added for preparation of the stock solution

in g mss_dil mass of stock solution added for preparation of dilution in g mdil_lot mass of dilution added for preparation of the lot in g mss total mass of stock solution in g mdil total mass of dilution in g mlot total mass of the lot in g ρlot density of the lot in g/l P purity of the standard K buoyancy correction Based on this formula the uncertainty budget can be prepared and all components be quantified. The following figure shows a typical distribution of the contributions, here for atrazine as an example. The main contribution results from the uncertainty of the concentration of the standard. The uncertainty of the concentration was taken from the certificate of the supplier.

Kmmm

mmPmc

lotdilss

lotlotdildilsssssub stlot ⋅⋅⋅

⋅⋅⋅⋅=

ρ___


All weighings were done as difference weighings. The uncertainty of these weighings were taken from the calibration certificate of the balance prepared by an accredited calibration laboratory. The determination of the density was also made using weighings (of the pycnome-ter). The above said also applies here. Temperature measurement was made with a calibrated thermometer. The purity of the used atrazine was taken from the certificate of the manufacturer. With all these uncertainty components the combined uncertain-ty, as described in the EURACHEM/CITAC-Guide „Quantifying Uncertainty in Analyt-ical Measurement“, was calculated using the sensitivity coefficients determined by partial derivation of the formula to the respective influence quantities. So traceability was assured by using calibrated balances and thermometers. Determination of the matrix content

Because the same matrix was used for preparation of all samples, the matrix content could be calculated from the mean values of the participants and the spiked amounts in a standard-addition-like way1,2. The uncertainties of the spiked amounts were known from the uncertainty budgets. The expanded uncertainties of the mean values of participants’ result were calculated according to ISO 13528 (Statistical Methods for Use in Proficiency Testing by Interla-boratory Comparisons) as

n

su R

mean ⋅⋅= 25,12

with: sR reproducibility standard deviation n number of data for this level 2 coverage factor for the expanded uncertainty 1,25 correction factor (according to ISO 13528 to be used for robust methods)

1 Rienitz, O., Schiel, D., Güttler, B., Koch, M., Borchers, U.: A convenient and economic approach to achieve SI-traceable reference values to be used in drinking-water interlaboratory comparisons. Ac-cred Qual Assur (2007) 12: 615-622. 2 Koch, M., Baumeister, F.: Traceable reference values for routine drinking water proficiency testing: first experiences. Accred Qual Assur (2008) 13: 77-82.

0 5E-11 1E-10 1,5E-10 2E-10 2,5E-10

weighing substance in g

purity

weighing in dilution in g

weighing in lot in g

density in g/l

total mass of stock solution in g

total mass of dilution in g

total mas lot in g

buoyancy correction

PT-WFD – priority pesticides page 12 The content of the matrix can be derived from a linear regression of means vs. spiked amounts. Since uncertainties of all data points were available for x- as well as y-direction a generalised least square regression was used as described in DIN EN 6143. The computer program B_LEAST (from BAM) was used for this purpose. With this method a value for matrix and its uncertainty are obtained. Because of sta-tistical variation of the input values the calculated matrix content might result in a negative value. From a scientific point of view this of course is nonsense. In those cases the matrix content is set to zero. The lower end of the uncertainty range of the matrix content also might be negative. Therefore the expanded uncertainty of the ma-trix content was set to the matrix content itself in this case. The matrix content is not directly traceable to national or international references, but it does not considerably compromise the traceability of the final content due to its comparably low contribu-tion. As stated above the matrix content in the present PT round was negligible for all parameters.

14. Internet These report also is available from the following internet address: http://www.aqsbw/pdf/report511.pdf

PT 5/11 - PT-WFD

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1 0,0713 0,67 0,0231 0,0178 25,00 0,1070 0,0357 50,00 -50,00 22 0 2 9,12 0,1381 0,66 0,0286 0,0345 25,00 0,2072 0,0691 50,00 -50,00 22 0 1 4,53 0,5845 0,65 0,1306 0,1461 25,00 0,8768 0,2923 50,00 -50,00 22 1 0 4,5

sum 66 1 3 6,1 Recovery and matrix content Slope of the regression line: 0,9159, recovery: 91,6 %neg. x-axis-intercept = matrix content: 0,0037 μg/lexpanded uncertainty of the matrix content: 0,0037 μg/l = 100 % page A-1 of A-89

aclonifen

aclonifen

0

0,1

0,2

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0,5

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0,7

-0,1 0 0,1 0,2 0,3 0,4 0,5 0,6 0,7

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PT 5/11 - PT-WFD

Relative standard deviation and tolerance limits The relative standard deviation, calculated with Algorithm A, reached the standard deviationfor proficiency assessment of 25 % at one concentration level. page A-2 of A-89

aclonifen

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30

35

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7

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%

aclonifen

-60

-40

-20

0

20

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60

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


tole

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PT 5/11 - PT-WFD

Method specific evaluation The values determined with HPLC-MS/MS - direct injection showed the closest distribution. page A-3 of A-89

used methods for aclonifen

36,36

31,82 31,82

0

5

10

15

20

25

30

35

40

HPLC-MS/MS - direct injection HPLC-MS/MS - extraction Others

perc

enta

ge

too low low correct high too high

HPLC-MS/MS - direct injection

HPLC-MS/MS - extraction

Others

010203040

50

60

70

80

90

100

freq

uenc

y in

%

method comparison aclonifen

PT 5/11 - PT-WFD

Comparison of means and reference valuesle

vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

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[%]

refe

renc

e va

lue

[μg/

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exp.

unc

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[μg/

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exp.

unc

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[%]

1 0,0704 0,0123 17,5 0,0713 0,0005 0,72 0,1321 0,0152 11,5 0,1381 0,0009 0,73 0,5305 0,0696 13,1 0,5845 0,0038 0,7

In the following figures there are no method specific values illustrated, because in all casesno more than 7 values were assessed as satisfactory. page A-4 of A-89

comparison of means and reference values

00,010,020,030,040,050,060,070,080,09

1

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PT 5/11 - PT-WFD

page A-5 of A-89


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PT 5/11 - PT-WFD

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1 0,0694 0,67 0,0111 0,0174 25,00 0,1041 0,0347 50,00 -50,00 29 0 1 3,42 0,2924 0,66 0,0490 0,0731 25,00 0,4386 0,1462 50,00 -50,00 29 0 2 6,93 0,5553 0,66 0,0940 0,1388 25,00 0,8330 0,2777 50,00 -50,00 29 0 1 3,4

sum 87 0 4 4,6 Recovery and matrix content Slope of the regression line: 1,000, recovery: 100 %neg. x-axis-intercept = matrix content: 0,0015 μg/lexpanded uncertainty of the matrix content: 0,0015 μg/l = 100 % page A-7 of A-89

alachlor

alachlor

0

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0,7

-0,1 0 0,1 0,2 0,3 0,4 0,5 0,6


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PT 5/11 - PT-WFD

Relative standard deviation and tolerance limits The relative standard deviation, calculated with Algorithm A, reached not the standard deviationfor proficiency assessment of 25 %. page A-8 of A-89

alachlor

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0 0,1 0,2 0,3 0,4 0,5 0,6


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-60

-40

-20

0

20

40

60

0 0,1 0,2 0,3 0,4 0,5 0,6


tole

ranc

e lim

its in

%

PT 5/11 - PT-WFD


used methods for alachlor

37,93

31,03 31,03

0

5

10

15

20

25

30

35

40

Others HPLC-MS/MS - direct injection HPLC-MS/MS - extraction

perc

enta

ge


Others



010

20

30

40

50

60

70

80

90

100

freq

uenc

y in

%

method comparison alachlor

PT 5/11 - PT-WFD


vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

refe

renc

e va

lue

[μg/

l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

1 0,0718 0,0051 7,2 0,0694 0,0005 0,72 0,2992 0,0228 7,6 0,2924 0,0019 0,73 0,5604 0,0436 7,8 0,5553 0,0036 0,7

page A-10 of A-89


00,010,020,030,040,050,060,070,080,09

1

level

mea

n in

μg/

l

overall mean reference valuesOthers

HPLC-MS/MS - direct injection HPLC-MS/MS - extraction

PT 5/11 - PT-WFD

page A-11 of A-89


00,050,1

0,150,2

0,250,3

0,350,4

2

level

mea

n in

μg/

l




0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

3

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0726 0,0061 8,434 0,0162 22,378 11 1 0 9,0912 0,3162 0,0318 10,051 0,0843 26,669 11 1 0 9,0913 0,5465 0,0599 10,962 0,1589 29,086 11 1 0 9,091

page A-12 of A-89

Others


0

5

10

15

20

25

30

35

1 2 3

level

rel.

stan

dard

dev

. in

%

overall mean OthersHPLC-MS/MS - direct injection HPLC-MS/MS - extraction

PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

2 0,3077 0,0089 2,9002 0,0214 6,9604 9 0 1 11,113 0,5733 0,0163 2,8468 0,0392 6,8322 9 0 0 0

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0691 0,0058 8,4323 0,014 20,238 9 0 1 11,112 0,284 0,0143 5,031 0,0343 12,074 9 0 1 11,11 page A-13 of A-89



PT 5/11 - PT-WFD

leve

l

assi

gned

val

ue [μ

g/l]

expa

nded

unc

erta

inty

of t

he

assi

gned

val

ue [%

]

stan

dard

dev

iatio

n, c

alcu

late

d us

ing

robu

st s

tatis

tics

[μg/

l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [μg

/l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [

%]

uppe

r tol

eran

ce li

mit

[μg/

l]

low

er to

lera

nce

limit

[μg/

l]

uppe

r tol

eran

ce li

mit

[%]

low

er to

lera

nce

limit

[%]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0781 0,67 0,0174 0,0195 25,00 0,1172 0,0391 50,00 -50,00 32 1 2 9,42 0,3583 0,66 0,0829 0,0896 25,00 0,5375 0,1792 50,00 -50,00 32 2 2 12,53 0,6151 0,66 0,1112 0,1538 25,00 0,9227 0,3076 50,00 -50,00 32 1 0 3,1


atrazine

atrazine

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

-0,1 0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


mea

n in

μg/

l

PT 5/11 - PT-WFD


atrazine

0

5

10

15

20

25

30

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


rel.

stan

dard

dev

iatio

n in

%

atrazine

-60

-40

-20

0

20

40

60

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


tole

ranc

e lim

its in

%

PT 5/11 - PT-WFD

Method specific evaluation The values determined with HPLC-MS/MS - direct injection showed the closest distribution.

page A-16 of A-89

used methods for atrazine

37,50 37,50

9,38 9,38

3,13 3,13

0

5

10

15

20

25

30

35

40

HPLC-MS/MS- direct

injection

HPLC-MS/MS- extraction

GC-MS/SPE Others GC-MS/LLE GC-PND/LLE

perc

enta

ge



HPLC-MS/MS - extractionGC-MS/SPEOthers

0102030

40

50

60

70

80

90

100

freq

uenc

y in

%

method comparison atrazine

PT 5/11 - PT-WFD


vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

refe

renc

e va

lue

[μg/

l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

1 0,0753 0,0077 10,2 0,0781 0,0005 0,72 0,3320 0,0367 11,0 0,3583 0,0024 0,73 0,5509 0,0492 8,9 0,6151 0,0041 0,7

page A-17 of A-89


00,010,020,030,040,050,060,070,080,09

1

level

mea

n in

μg/

l

overall mean reference valuesHPLC-MS/MS - direct injection


PT 5/11 - PT-WFD

page A-18 of A-89


00,050,1

0,150,2

0,250,3

0,350,4

2

level

mea

n in

μg/

l




0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

3

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0744 0,0045 5,985 0,0123 16,586 12 1 0 8,3332 0,3374 0,0151 4,4861 0,0419 12,432 12 1 0 8,3333 0,5807 0,0259 4,4675 0,0719 12,381 12 2 0 16,67

page A-19 of A-89



0

5

10

15

20

25

30

35

1 2 3

level

rel.

stan

dard

dev

. in

%

overall mean HPLC-MS/MS - direct injection HPLC-MS/MS - extraction

PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,073 0,008 10,965 0,0222 30,386 12 1 1 16,672 0,3411 0,0328 9,624 0,091 26,671 12 1 0 8,3333 0,546 0,0432 7,92 0,1198 21,949 12 1 0 8,333 page A-20 of A-89


PT 5/11 - PT-WFD

leve

l

assi

gned

val

ue [μ

g/l]

expa

nded

unc

erta

inty

of t

he

assi

gned

val

ue [%

]

stan

dard

dev

iatio

n, c

alcu

late

d us

ing

robu

st s

tatis

tics

[μg/

l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [μg

/l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [

%]

uppe

r tol

eran

ce li

mit

[μg/

l]

low

er to

lera

nce

limit

[μg/

l]

uppe

r tol

eran

ce li

mit

[%]

low

er to

lera

nce

limit

[%]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0723 0,67 0,0149 0,0181 25,00 0,1085 0,0362 50,00 -50,00 23 2 1 13,02 0,3060 0,66 0,0496 0,0765 25,00 0,4590 0,1530 50,00 -50,00 23 0 0 0,03 0,5154 0,66 0,0790 0,1289 25,00 0,7731 0,2577 50,00 -50,00 23 0 0 0,0

sum 69 2 1 4,3 Recovery and matrix content Slope of the regression line: 0,7554, recovery: 75,5 %neg. x-axis-intercept = matrix content: 0 μg/lexpanded uncertainty of the matrix content: 0,0011 μg/l = 0 % page A-21 of A-89

bifenox

bifenox

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

0,45

0,5

0 0,1 0,2 0,3 0,4 0,5 0,6


mea

n in

μg/

l

PT 5/11 - PT-WFD


bifenox

0

5

10

15

20

25

30

0 0,1 0,2 0,3 0,4 0,5 0,6


rel.

stan

dard

dev

iatio

n in

%

bifenox

-60

-40

-20

0

20

40

60

0 0,1 0,2 0,3 0,4 0,5 0,6


tole

ranc

e lim

its in

%

PT 5/11 - PT-WFD

Method specific evaluation The values determined with HPLC-MS/MS - direct injection showed the closest distribution.Because of the low recovery, all methods showed lower values, especially HPLC-MS/MSafter extraction. Incomplete extraction seems to be the major problem. page A-23 of A-89

used methods for bifenox

39,13 39,13

21,74

0

5

10

15

20

25

30

35

40

45

HPLC-MS/MS - extraction Others HPLC-MS/MS - direct injection

perc

enta

ge



Others


0

10

20

30

40

50

60

70

80

90

freq

uenc

y in

%

method comparison bifenox

PT 5/11 - PT-WFD


vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

refe

renc

e va

lue

[μg/

l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

1 0,0551 0,0078 14,1 0,0723 0,0005 0,72 0,2343 0,0259 11,0 0,3060 0,0020 0,73 0,3901 0,0412 10,6 0,5154 0,0034 0,7

page A-24 of A-89


0

0,01

0,02

0,03

0,04

0,05

0,06

0,07

0,08

1

level

mea

n in

μg/

l

overall mean reference values HPLC-MS/MS - extraction Others

PT 5/11 - PT-WFD

page A-25 of A-89


0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

2

level

mea

n in

μg/

l



0

0,1

0,2

0,3

0,4

0,5

0,6

3

level

mea

n in

μg/

l


PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

2 0,2045 0,0119 5,8314 0,0286 13,995 9 0 1 11,113 0,3479 0,0342 9,8344 0,0821 23,603 9 0 1 11,11

page A-26 of A-89



0

5

10

15

20

25

30

35

40

1 2 3

level

rel.

stan

dard

dev

. in

%

overall mean HPLC-MS/MS - extraction Others

PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0534 0,0065 12,202 0,0157 29,285 9 0 1 11,112 0,2605 0,0401 15,386 0,0962 36,926 9 0 1 11,113 0,3959 0,0499 12,612 0,1198 30,268 9 0 1 11,11 page A-27 of A-89

Others

PT 5/11 - PT-WFD

leve

l

assi

gned

val

ue [μ

g/l]

expa

nded

unc

erta

inty

of t

he

assi

gned

val

ue [%

]

stan

dard

dev

iatio

n, c

alcu

late

d us

ing

robu

st s

tatis

tics

[μg/

l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [μg

/l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [

%]

uppe

r tol

eran

ce li

mit

[μg/

l]

low

er to

lera

nce

limit

[μg/

l]

uppe

r tol

eran

ce li

mit

[%]

low

er to

lera

nce

limit

[%]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0635 1,14 0,0133 0,0159 25,00 0,0953 0,0318 50,00 -50,00 26 0 3 11,52 0,1360 1,14 0,0274 0,0340 25,00 0,2040 0,0680 50,00 -50,00 26 1 2 11,53 0,4750 1,14 0,0721 0,1188 25,00 0,7125 0,2375 50,00 -50,00 26 1 0 3,8


chlorfenvinphos

chlorfenvinphos

0

0,1

0,2

0,3

0,4

0,5

0,6

-0,1 0 0,1 0,2 0,3 0,4 0,5 0,6


mea

n in

μg/

l

PT 5/11 - PT-WFD


chlorfenvinphos

0

5

10

15

20

25

30

0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 0,45 0,5


rel.

stan

dard

dev

iatio

n in

%

chlorfenvinphos

-60

-40

-20

0

20

40

60

0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 0,45 0,5


tole

ranc

e lim

its in

%

PT 5/11 - PT-WFD

Method specific evaluation The differences between the methods were not significant. page A-30 of A-89

used methods for chlorfenvinphos

34,62 34,62

30,77

0

5

10

15

20

25

30

35

40

HPLC-MS/MS - direct injection HPLC-MS/MS - extraction Others

perc

enta

ge




Others

0

10

20

30

40

50

60

70

80

90

100

freq

uenc

y in

%

method comparison chlorfenvinphos

PT 5/11 - PT-WFD


vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

refe

renc

e va

lue

[μg/

l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

1 0,0687 0,0065 9,5 0,0635 0,0007 1,12 0,1434 0,0134 9,4 0,1360 0,0015 1,13 0,4749 0,0354 7,4 0,4750 0,0054 1,1

page A-31 of A-89


00,010,020,030,040,050,060,070,08

1

level

mea

n in

μg/

l


HPLC-MS/MS - extraction Others

PT 5/11 - PT-WFD

page A-32 of A-89


00,020,040,060,080,1

0,120,140,160,18

2

level

mea

n in

μg/

l




0

0,1

0,2

0,3

0,4

0,5

0,6

3

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

2 0,1542 0,0118 7,6767 0,0284 18,424 9 0 1 11,113 0,5148 0,0361 7,0047 0,0865 16,811 9 0 1 11,11

page A-33 of A-89



0

5

10

15

20

25

30

1 2 3

level

rel.

stan

dard

dev

. in

%

overall mean HPLC-MS/MS - direct injectionHPLC-MS/MS - extraction Others

PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0646 0,0052 8,1083 0,0126 19,46 9 0 1 11,11

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

3 0,4607 0,0505 10,964 0,1143 24,81 8 0 0 0 page A-34 of A-89


Others

PT 5/11 - PT-WFD

leve

l

assi

gned

val

ue [μ

g/l]

expa

nded

unc

erta

inty

of t

he

assi

gned

val

ue [%

]

stan

dard

dev

iatio

n, c

alcu

late

d us

ing

robu

st s

tatis

tics

[μg/

l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [μg

/l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [

%]

uppe

r tol

eran

ce li

mit

[μg/

l]

low

er to

lera

nce

limit

[μg/

l]

uppe

r tol

eran

ce li

mit

[%]

low

er to

lera

nce

limit

[%]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0606 0,67 0,0212 0,0152 25,00 0,0909 0,0303 50,00 -50,00 25 1 3 16,02 0,3462 0,66 0,1120 0,0866 25,00 0,5193 0,1731 50,00 -50,00 26 1 3 15,43 0,5948 0,66 0,2267 0,1487 25,00 0,8922 0,2974 50,00 -50,00 26 1 4 19,2


chlorpyrifos-ethyl

chlorpyrifos-ethyl

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

-0,1 0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


mea

n in

μg/

l

PT 5/11 - PT-WFD

Relative standard deviation and tolerance limits The relative standard deviation, calculated with Algorithm A, reached the standard deviationfor proficiency assessment of 25 % at all concentration levels. page A-36 of A-89

chlorpyrifos-ethyl

0

5

10

15

20

25

30

35

40

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


rel.

stan

dard

dev

iatio

n in

%

chlorpyrifos-ethyl

-60

-40

-20

0

20

40

60

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


tole

ranc

e lim

its in

%

PT 5/11 - PT-WFD

Method specific evaluation The HPLC-MS/MS -method with direct injection delivered more higher values and the HPLC-MS/MS - method after extraction more lower values. page A-37 of A-89

used methods for chlorpyrifos-ethyl

38,96

31,17 29,87

0

5

10

15

20

25

30

35

40

45

Others HPLC-MS/MS - direct injection HPLC-MS/MS - extraction

perc

enta

ge


Others

HPLC-MS/MS - direct injectionHPLC-MS/MS - extraction

0

10

20

30

40

50

60

freq

uenc

y in

%

method comparison chlorpyrifos-ethyl

PT 5/11 - PT-WFD


vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

refe

renc

e va

lue

[μg/

l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

1 0,0671 0,0106 15,8 0,0606 0,0004 0,72 0,3552 0,0549 15,5 0,3462 0,0023 0,73 0,6005 0,1111 18,5 0,5948 0,0039 0,7

page A-38 of A-89


00,010,020,030,040,050,060,070,080,09

1

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

page A-39 of A-89


00,050,1

0,150,2

0,250,3

0,350,4

0,450,5

2

level

mea

n in

μg/

l




00,10,20,30,40,50,60,70,80,9

3

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0596 0,0078 13,067 0,0197 33,057 10 0 2 202 0,3062 0,0298 9,7413 0,0755 24,644 10 0 1 103 0,5575 0,0895 16,049 0,2264 40,601 10 0 1 10

page A-40 of A-89

Others


0

10

20

30

40

50

60

70

1 2 3

level

rel.

stan

dard

dev

. in

%

overall mean OthersHPLC-MS/MS - direct injection HPLC-MS/MS - extraction

PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

2 0,4146 0,0504 12,148 0,114 27,487 8 0 0 03 0,6992 0,0795 11,368 0,1799 25,723 8 0 0 0

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

2 0,3357 0,0914 27,225 0,2068 61,603 8 0 0 03 0,5281 0,152 28,784 0,344 65,13 8 0 0 0 page A-41 of A-89



PT 5/11 - PT-WFD

leve

l

assi

gned

val

ue [μ

g/l]

expa

nded

unc

erta

inty

of t

he

assi

gned

val

ue [%

]

stan

dard

dev

iatio

n, c

alcu

late

d us

ing

robu

st s

tatis

tics

[μg/

l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [μg

/l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [

%]

uppe

r tol

eran

ce li

mit

[μg/

l]

low

er to

lera

nce

limit

[μg/

l]

uppe

r tol

eran

ce li

mit

[%]

low

er to

lera

nce

limit

[%]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0810 0,67 0,0169 0,0203 25,00 0,1215 0,0405 50,00 -50,00 28 0 2 7,12 0,1962 0,66 0,0348 0,0491 25,00 0,2943 0,0981 50,00 -50,00 28 0 1 3,63 0,4550 0,66 0,0774 0,1138 25,00 0,6825 0,2275 50,00 -50,00 28 0 0 0,0


diuron

diuron

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

0,45

0,5

-0,1 0 0,1 0,2 0,3 0,4 0,5


mea

n in

μg/

l

PT 5/11 - PT-WFD


diuron

0

5

10

15

20

25

30

0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 0,45 0,5


rel.

stan

dard

dev

iatio

n in

%

diuron

-60

-40

-20

0

20

40

60

0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 0,45 0,5


tole

ranc

e lim

its in

%

PT 5/11 - PT-WFD

Method specific evaluation The differences between the methods were not significant. page A-44 of A-89

used methods for diuron

46,43

39,29

10,71

3,57

0

5

10

15

20

25

30

35

40

45

50

HPLC-MS/MS - directinjection

HPLC-MS/MS -extraction

Others HPLC-UV/SPE

perc

enta

ge




Others

01020304050

60

70

80

90

100

freq

uenc

y in

%

method comparison diuron

PT 5/11 - PT-WFD


vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

refe

renc

e va

lue

[μg/

l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

1 0,0821 0,0080 9,7 0,0810 0,0005 0,72 0,1897 0,0164 8,7 0,1962 0,0013 0,73 0,4323 0,0366 8,5 0,4550 0,0030 0,7

page A-45 of A-89


00,010,020,030,040,050,060,070,080,090,1

1

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

page A-46 of A-89


0

0,05

0,1

0,15

0,2

0,25

2

level

mea

n in

μg/

l




00,050,1

0,150,2

0,250,3

0,350,4

0,450,5

3

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0823 0,0031 3,7405 0,0089 10,789 13 2 0 15,382 0,1951 0,0085 4,3369 0,0244 12,509 13 1 0 7,6923 0,4447 0,0177 3,9789 0,051 11,477 13 1 0 7,692

page A-47 of A-89



0

5

10

15

20

25

30

1 2 3

level

rel.

stan

dard

dev

. in

%


PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0828 0,0087 10,449 0,023 27,724 11 0 2 18,182 0,1831 0,0174 9,525 0,0463 25,273 11 0 2 18,183 0,4285 0,0423 9,8658 0,1122 26,177 11 0 0 0 page A-48 of A-89


PT 5/11 - PT-WFD

leve

l

assi

gned

val

ue [μ

g/l]

expa

nded

unc

erta

inty

of t

he

assi

gned

val

ue [%

]

stan

dard

dev

iatio

n, c

alcu

late

d us

ing

robu

st s

tatis

tics

[μg/

l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [μg

/l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [

%]

uppe

r tol

eran

ce li

mit

[μg/

l]

low

er to

lera

nce

limit

[μg/

l]

uppe

r tol

eran

ce li

mit

[%]

low

er to

lera

nce

limit

[%]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0772 0,67 0,0108 0,0193 25,00 0,1158 0,0386 50,00 -50,00 29 0 1 3,42 0,2685 0,66 0,0383 0,0671 25,00 0,4028 0,1343 50,00 -50,00 29 0 1 3,43 0,5596 0,66 0,0719 0,1399 25,00 0,8394 0,2798 50,00 -50,00 29 0 1 3,4

sum 87 0 3 3,4 Recovery and matrix content Slope of the regression line: 0,950, recovery: 95 %neg. x-axis-intercept = matrix content: 0,0012 μg/lexpanded uncertainty of the matrix content: 0,0012 μg/l = 100 % page A-49 of A-89

isoproturon

isoproturon

0

0,1

0,2

0,3

0,4

0,5

0,6

-0,1 0 0,1 0,2 0,3 0,4 0,5 0,6


mea

n in

μg/

l

PT 5/11 - PT-WFD


isoproturon

0

5

10

15

20

25

30

0 0,1 0,2 0,3 0,4 0,5 0,6


rel.

stan

dard

dev

iatio

n in

%

isoproturon

-60

-40

-20

0

20

40

60

0 0,1 0,2 0,3 0,4 0,5 0,6


tole

ranc

e lim

its in

%

PT 5/11 - PT-WFD


used methods for isoproturon

44,8341,38

10,34

3,45

0

5

10

15

20

25

30

35

40

45

50



Others HPLC-UV/SPE

perc

enta

ge



HPLC-MS/MS - extractionOthers

0102030405060708090

100

freq

uenc

y in

%

method comparison isoproturon

PT 5/11 - PT-WFD


vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

refe

renc

e va

lue

[μg/

l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

1 0,0745 0,0050 6,7 0,0772 0,0005 0,72 0,2670 0,0178 6,7 0,2685 0,0018 0,73 0,5325 0,0334 6,3 0,5596 0,0037 0,7

page A-52 of A-89


00,010,020,030,040,050,060,070,080,09

1

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

page A-53 of A-89


0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

2

level

mea

n in

μg/

l




0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

3

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0735 0,0045 6,1057 0,0129 17,612 13 1 0 7,6922 0,265 0,0062 2,3525 0,018 6,7856 13 1 1 15,383 0,5435 0,0127 2,3302 0,0365 6,7212 13 2 1 23,08

page A-54 of A-89



02468

101214161820

1 2 3

level

rel.

stan

dard

dev

. in

%


PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0725 0,0036 4,9361 0,0099 13,679 12 0 3 252 0,274 0,016 5,8453 0,0444 16,199 12 0 4 33,333 0,5593 0,0362 6,471 0,1003 17,933 12 0 3 25 page A-55 of A-89


PT 5/11 - PT-WFD

leve

l

assi

gned

val

ue [μ

g/l]

expa

nded

unc

erta

inty

of t

he

assi

gned

val

ue [%

]

stan

dard

dev

iatio

n, c

alcu

late

d us

ing

robu

st s

tatis

tics

[μg/

l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [μg

/l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [

%]

uppe

r tol

eran

ce li

mit

[μg/

l]

low

er to

lera

nce

limit

[μg/

l]

uppe

r tol

eran

ce li

mit

[%]

low

er to

lera

nce

limit

[%]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0635 0,67 0,0225 0,0159 25,00 0,0953 0,0318 50,00 -50,00 21 1 3 19,02 0,2125 0,66 0,0706 0,0531 25,00 0,3188 0,1063 50,00 -50,00 21 1 2 14,33 0,5534 0,66 0,1665 0,1384 25,00 0,8301 0,2767 50,00 -50,00 21 2 2 19,0


quinoxyfen

quinoxyfen

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

-0,1 0 0,1 0,2 0,3 0,4 0,5 0,6


mea

n in

μg/

l

PT 5/11 - PT-WFD

Relative standard deviation and tolerance limits The relative standard deviation, calculated with Algorithm A, reached the standard deviationfor proficiency assessment of 25 % at all concentration levels. page A-57 of A-89

quinoxyfen

0

5

10

15

20

25

30

35

0 0,1 0,2 0,3 0,4 0,5 0,6


rel.

stan

dard

dev

iatio

n in

%

quinoxyfen

-60

-40

-20

0

20

40

60

0 0,1 0,2 0,3 0,4 0,5 0,6


tole

ranc

e lim

its in

%

PT 5/11 - PT-WFD

Method specific evaluation The HPLC-MS/MS method after direct injection delivered more higher values, but it must be consideredthat the total number of values of 63 is from a statistical point of view very low. page A-58 of A-89

used methods for quinoxyfen

38,10 38,10

23,81

0

5

10

15

20

25

30

35

40



perc

enta

ge



HPLC-MS/MS - extractionOthers

0

10

20

30

40

50

60

70

80

freq

uenc

y in

%

method comparison quinoxyfen

PT 5/11 - PT-WFD


vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

refe

renc

e va

lue

[μg/

l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

1 0,0695 0,0123 17,7 0,0635 0,0004 0,72 0,2163 0,0385 17,8 0,2125 0,0014 0,73 0,5413 0,0908 16,8 0,5534 0,0036 0,7

page A-59 of A-89


00,010,020,030,040,050,060,070,080,09

1

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

page A-60 of A-89


0

0,05

0,1

0,15

0,2

0,25

0,3

2

level

mea

n in

μg/

l




00,10,20,30,40,50,60,70,8

3

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

3 0,6258 0,1275 20,382 0,2886 46,119 8 0 0 0

page A-61 of A-89



0

10

20

30

40

50

60

70

80

1 2 3

level

rel.

stan

dard

dev

. in

%


PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

2 0,1838 0,0554 30,15 0,1254 68,221 8 0 0 03 0,4869 0,1123 23,065 0,2541 52,19 8 0 0 0 page A-62 of A-89


PT 5/11 - PT-WFD

leve

l

assi

gned

val

ue [μ

g/l]

expa

nded

unc

erta

inty

of t

he

assi

gned

val

ue [%

]

stan

dard

dev

iatio

n, c

alcu

late

d us

ing

robu

st s

tatis

tics

[μg/

l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [μg

/l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [

%]

uppe

r tol

eran

ce li

mit

[μg/

l]

low

er to

lera

nce

limit

[μg/

l]

uppe

r tol

eran

ce li

mit

[%]

low

er to

lera

nce

limit

[%]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0704 0,67 0,0191 0,0176 25,00 0,1056 0,0352 50,00 -50,00 32 1 4 15,62 0,3500 0,66 0,0665 0,0875 25,00 0,5250 0,1750 50,00 -50,00 32 1 3 12,53 0,6140 0,66 0,1178 0,1535 25,00 0,9210 0,3070 50,00 -50,00 32 1 2 9,4


simazine

simazine

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

-0,1 0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


mea

n in

μg/

l

PT 5/11 - PT-WFD


simazine

0

5

10

15

20

25

30

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


rel.

stan

dard

dev

iatio

n in

%

simazine

-60

-40

-20

0

20

40

60

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


tole

ranc

e lim

its in

%

PT 5/11 - PT-WFD


used methods for simazine

37,50 37,50

9,38 9,38

3,13 3,13

0

5

10

15

20

25

30

35

40

HPLC-MS/MS -

directinjection


GC-MS/SPE Others GC-MS/LLE GC-PND/LLE

perc

enta

ge



HPLC-MS/MS - extractionGC-MS/SPEOthers

0102030405060708090

100

freq

uenc

y in

%

method comparison simazine

PT 5/11 - PT-WFD


vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

refe

renc

e va

lue

[μg/

l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

1 0,0695 0,0084 12,2 0,0704 0,0005 0,72 0,3269 0,0294 9,0 0,3500 0,0023 0,73 0,5734 0,0520 9,1 0,6140 0,0040 0,7

page A-66 of A-89


00,010,020,030,040,050,060,070,080,090,1

1

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

page A-67 of A-89


00,050,1

0,150,2

0,250,3

0,350,4

2

level

mea

n in

μg/

l




00,10,20,30,40,50,60,70,8

3

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,069 0,0031 4,5403 0,0087 12,583 12 1 1 16,672 0,3352 0,012 3,5837 0,0333 9,9314 12 1 1 16,673 0,5954 0,0156 2,6227 0,0433 7,2682 12 1 0 8,333

page A-68 of A-89



05

101520253035404550

1 2 3

level

rel.

stan

dard

dev

. in

%


PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0794 0,0136 17,135 0,0377 47,486 12 0 2 16,672 0,3209 0,0304 9,4818 0,0843 26,277 12 0 4 33,333 0,6034 0,0721 11,944 0,1997 33,1 12 0 2 16,67 page A-69 of A-89


PT 5/11 - PT-WFD

leve

l

assi

gned

val

ue [μ

g/l]

expa

nded

unc

erta

inty

of t

he

assi

gned

val

ue [%

]

stan

dard

dev

iatio

n, c

alcu

late

d us

ing

robu

st s

tatis

tics

[μg/

l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [μg

/l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [

%]

uppe

r tol

eran

ce li

mit

[μg/

l]

low

er to

lera

nce

limit

[μg/

l]

uppe

r tol

eran

ce li

mit

[%]

low

er to

lera

nce

limit

[%]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0622 0,67 0,0130 0,0156 25,00 0,0933 0,0311 50,00 -50,00 30 0 2 6,72 0,2766 0,66 0,0454 0,0692 25,00 0,4149 0,1383 50,00 -50,00 30 1 2 10,03 0,4888 0,66 0,0935 0,1222 25,00 0,7332 0,2444 50,00 -50,00 30 1 2 10,0


terbutryn

terbutryn

0

0,1

0,2

0,3

0,4

0,5

0,6

-0,1 0 0,1 0,2 0,3 0,4 0,5 0,6


mea

n in

μg/

l

PT 5/11 - PT-WFD


terbutryn

0

5

10

15

20

25

30

0 0,1 0,2 0,3 0,4 0,5 0,6


rel.

stan

dard

dev

iatio

n in

%

terbutryn

-60

-40

-20

0

20

40

60

0 0,1 0,2 0,3 0,4 0,5 0,6


tole

ranc

e lim

its in

%

PT 5/11 - PT-WFD

Method specific evaluation The values determined with HPLC-MS/MS - direct injection showed the closest distribution.

page A-72 of A-89

used methods for terbutryn

40,0036,67

10,006,67

3,33 3,33

05

1015202530354045


HPLC-MS/MS -

directinjection

Others GC-MS/SPE GC-MS/LLE GC-PND/LLE

perc

enta

ge



HPLC-MS/MS - direct injection0

102030

40

50

60

70

80

90

freq

uenc

y in

%

method comparison terbutryn

PT 5/11 - PT-WFD


vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

refe

renc

e va

lue

[μg/

l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

1 0,0652 0,0059 9,1 0,0622 0,0004 0,72 0,2758 0,0207 7,5 0,2766 0,0018 0,73 0,4820 0,0427 8,9 0,4888 0,0032 0,7

page A-73 of A-89


00,010,020,030,040,050,060,070,08

1

level

mea

n in

μg/

l

overall mean reference valuesHPLC-MS/MS - extraction


PT 5/11 - PT-WFD

page A-74 of A-89


0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

2

level

mea

n in

μg/

l




0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

3

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0672 0,0048 7,1498 0,0133 19,814 12 0 3 252 0,2679 0,0135 5,0524 0,0375 14,002 12 0 3 253 0,5411 0,0542 10,019 0,1502 27,766 12 0 0 0

page A-75 of A-89



0

5

10

15

20

25

30

1 2 3

level

rel.

stan

dard

dev

. in

%

overall mean HPLC-MS/MS - extraction HPLC-MS/MS - direct injection

PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0653 0,0031 4,778 0,0083 12,677 11 1 1 18,182 0,2774 0,0124 4,4724 0,0329 11,867 11 1 1 18,183 0,477 0,0168 3,524 0,0446 9,3503 11 1 0 9,091 page A-76 of A-89


PT 5/11 - PT-WFD

leve

l

assi

gned

val

ue [μ

g/l]

expa

nded

unc

erta

inty

of t

he

assi

gned

val

ue [%

]

stan

dard

dev

iatio

n, c

alcu

late

d us

ing

robu

st s

tatis

tics

[μg/

l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [μg

/l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [

%]

uppe

r tol

eran

ce li

mit

[μg/

l]

low

er to

lera

nce

limit

[μg/

l]

uppe

r tol

eran

ce li

mit

[%]

low

er to

lera

nce

limit

[%]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0678 0,67 0,0169 0,0170 25,00 0,1017 0,0339 50,00 -50,00 23 1 3 17,42 0,3189 0,66 0,0666 0,0797 25,00 0,4784 0,1595 50,00 -50,00 23 1 2 13,03 0,5821 0,65 0,1005 0,1455 25,00 0,8732 0,2911 50,00 -50,00 23 0 2 8,7


trifluralin

trifluralin

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

-0,1 0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


mea

n in

μg/

l

PT 5/11 - PT-WFD


trifluralin

0

5

10

15

20

25

30

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


rel.

stan

dard

dev

iatio

n in

%

trifluralin

-60

-40

-20

0

20

40

60

0 0,1 0,2 0,3 0,4 0,5 0,6 0,7


tole

ranc

e lim

its in

%

PT 5/11 - PT-WFD

Method specific evaluation The values determined with the GC-MS-methods delivered the closest distribution.All values analysed with the HPLC were too low. page A-79 of A-89

used methods for trifluralin

39,13

30,43

17,39

8,70

4,35

0

5

10

15

20

25

30

35

40

45

GC-MS/SPE GC-MS/LLE Others HPLC-MS/MS -extraction

GC-PND/LLE

perc

enta

ge


GC-MS/SPE

GC-MS/LLEOthersHPLC-MS/MS - extraction

0102030405060708090

100

freq

uenc

y in

%

method comparison trifluralin

PT 5/11 - PT-WFD


vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

refe

renc

e va

lue

[μg/

l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

1 0,0639 0,0088 13,8 0,0678 0,0005 0,72 0,2774 0,0347 12,5 0,3189 0,0021 0,73 0,5341 0,0524 9,8 0,5821 0,0038 0,7

page A-80 of A-89


0

0,01

0,02

0,03

0,04

0,05

0,06

0,07

0,08

1

level

mea

n in

μg/

l

overall mean reference values GC-MS/SPE

PT 5/11 - PT-WFD

page A-81 of A-89


0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

2

level

mea

n in

μg/

l



0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

3

level

mea

n in

μg/

l


PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

2 0,2887 0,0342 11,852 0,0821 28,444 9 0 1 11,113 0,5446 0,0495 9,0828 0,1187 21,799 9 0 1 11,11 page A-82 of A-89

GC-MS/SPE


0

5

10

15

20

25

30

1 2 3

level

rel.

stan

dard

dev

. in

%

overall mean GC-MS/SPE

PT 5/11 - PT-WFD

leve

l

assi

gned

val

ue [μ

g/l]

expa

nded

unc

erta

inty

of t

he

assi

gned

val

ue [%

]

stan

dard

dev

iatio

n, c

alcu

late

d us

ing

robu

st s

tatis

tics

[μg/

l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [μg

/l]

stan

dard

dev

iatio

n fo

r pro

ficie

ncy

asse

ssm

ent [

%]

uppe

r tol

eran

ce li

mit

[μg/

l]

low

er to

lera

nce

limit

[μg/

l]

uppe

r tol

eran

ce li

mit

[%]

low

er to

lera

nce

limit

[%]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0648 0,67 0,0100 0,0162 25,00 0,0972 0,0324 50,00 -50,00 24 2 1 12,52 0,2775 0,66 0,0519 0,0694 25,00 0,4163 0,1388 50,00 -50,00 24 2 1 12,53 0,4621 0,66 0,0733 0,1155 25,00 0,6932 0,2311 50,00 -50,00 24 1 1 8,3


cybutryne

cybutryne

0

0,1

0,2

0,3

0,4

0,5

0,6

-0,1 0 0,1 0,2 0,3 0,4 0,5


mea

n in

μg/

l

PT 5/11 - PT-WFD


cybutryne

0

5

10

15

20

25

30

0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 0,45 0,5


rel.

stan

dard

dev

iatio

n in

%

cybutryne

-60

-40

-20

0

20

40

60

0 0,05 0,1 0,15 0,2 0,25 0,3 0,35 0,4 0,45 0,5


tole

ranc

e lim

its in

%

PT 5/11 - PT-WFD


used methods for cybutryne

45,83

37,50

16,67

0

5

10

15

20

25

30

35

40

45

50



perc

enta

ge




Others

01020304050607080

90

100

freq

uenc

y in

%

method comparison cybutryne

PT 5/11 - PT-WFD


vel

mea

n [μ

g/l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

refe

renc

e va

lue

[μg/

l]

exp.

unc

erta

inty

[μg/

l]

exp.

unc

erta

inty

[%]

1 0,0666 0,0051 7,6 0,0648 0,0004 0,72 0,2805 0,0265 9,4 0,2775 0,0018 0,73 0,4462 0,0374 8,4 0,4621 0,0030 0,7

page A-86 of A-89


00,010,020,030,040,050,060,070,08

1

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

page A-87 of A-89


0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

2

level

mea

n in

μg/

l




0

0,1

0,2

0,3

0,4

0,5

0,6

3

level

mea

n in

μg/

l



PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

1 0,0682 0,002 2,9023 0,0053 7,7007 11 1 1 18,182 0,2933 0,0108 3,6717 0,0286 9,7421 11 1 1 18,183 0,4758 0,0211 4,4389 0,056 11,778 11 0 0 0

page A-88 of A-89



0

10

20

30

40

50

60

1 2 3

level

rel.

stan

dard

dev

. in

%


PT 5/11 - PT-WFD

leve

l

robu

st m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[μg/

l]

exp.

unc

erta

inty

of t

he m

ean

[%]

robu

st s

tand

ard

devi

atio

n [μ

g/l]

robu

st s

tand

ard

devi

atio

n [%

]

num

ber o

f res

ults

out b

elow

out a

bove

out [

%]

2 0,2646 0,0569 21,506 0,1366 51,614 9 0 1 11,11 page A-89 of A-89


PT 5/11 - PT-WFD

page B-1 of B-7

aclonifen - exp. measurement uncertainty

0%

10%

20%

30%

40%

50%

60%

exp

. mea

sure

men

t u

nce

rtai

nty

alachlor - exp. measurement uncertainty

0%

10%

20%

30%

40%

50%

60%

70%

exp

. mea

sure

men

t u

nce

rtai

nty

PT 5/11 - PT-WFD

page B-2 of B-7

atrazine - exp. measurement uncertainty

0%

5%

10%

15%

20%

25%

30%

35%

40%

45%

50%

exp

. mea

sure

men

t u

nce

rtai

nty

bifenox - exp. measurement uncertainty

0%

5%

10%

15%

20%

25%

30%

35%

40%

45%

exp

. mea

sure

men

t u

nce

rtai

nty

PT 5/11 - PT-WFD

page B-3 of B-7

chlorfenvinphos - exp. measurement uncertainty

0%

10%

20%

30%

40%

50%

60%

70%

exp

. mea

sure

men

t u

nce

rtai

nty

chlorpyrifos-ethyl - exp. measurement uncertainty

0%

5%

10%

15%

20%

25%

30%

35%

40%

45%

50%

exp

. mea

sure

men

t u

nce

rtai

nty

PT 5/11 - PT-WFD

page B-4 of B-7

diuron - exp. measurement uncertainty

0%

5%

10%

15%

20%

25%

30%

35%

40%

45%

50%

exp

. mea

sure

men

t u

nce

rtai

nty

isoproturon - exp. measurement uncertainty

0%

5%

10%

15%

20%

25%

30%

35%

exp

. mea

sure

men

t u

nce

rtai

nty

PT 5/11 - PT-WFD

page B-5 of B-7

quinoxyfen - exp. measurement uncertainty

0%

5%

10%

15%

20%

25%

30%

35%

40%

exp

. mea

sure

men

t u

nce

rtai

nty

simazine - exp. measurement uncertainty

0%

20%

40%

60%

80%

100%

120%

140%

160%

exp

. mea

sure

men

t u

nce

rtai

nty

PT 5/11 - PT-WFD

page B-6 of B-7

terbutryn - exp. measurement uncertainty

0%

10%

20%

30%

40%

50%

60%

exp

. mea

sure

men

t u

nce

rtai

nty

trifluralin - exp. measurement uncertainty

0%

5%

10%

15%

20%

25%

30%

35%

40%

45%

50%

exp

. mea

sure

men

t u

nce

rtai

nty

PT 5/11 - PT-WFD

page B-7 of B-7

cybutryne - exp. measurement uncertainty

0%

10%

20%

30%

40%

50%

60%

exp

. mea

sure

men

t u

nce

rtai

nty

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,07 -0,1 s6 0,086 0,8 s8 0,071 0,0 s9 0,069 -0,1 s

10 0,051 -1,1 s11 0,0691 0,024 -0,2 -0,1 s13 0,045 -1,5 s15 0,0766 0,3 s17 0,0782 0,029 0,5 0,4 s18 0,08 0,5 s20 0,043 0,013 -4,4 -1,6 s22 0,07762 0,023 0,5 0,4 s23 0,04243 -1,6 s29 0,08 0,5 s30 0,07714 0,3 s31 0,052 0,01 -3,9 -1,1 s32 0,109 0,001 68,1 2,1 q35 0,059 0,018 -1,4 -0,7 s36 0,131 3,3 u38 0,056 -0,9 s39 0,0372 -1,9 s41 0,104 1,8 s

page C-1 of C-117

assigned value [µg/l]*upper tolerance limit [µg/l]lower tolerance limit [µg/l]

* The stated uncertainty of the assigned value is the expanded uncertainty with a coverage factor k=2 corresponding to a confidence level of about 95%

aclonifen - 10,07130,107

0,03565

± 0,00047PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-2 of C-117

aclonifen - 1

0

0,02

0,04

0,06

0,08

0,1

0,12

0,1439 23 20 13 10 31 38 35 9 11 1 8 15 30 22 17 18 29 6 41 32 36

lab code

con

cen

trat

ion

in µ

g/l

aclonifen - 1

-3

-2

-1

0

1

2

3

4

39 23 20 13 10 31 38 35 9 11 1 8 15 30 22 17 18 29 6 41 32 36

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-3 of C-117

aclonifen - 1

0

0,005

0,01

0,015

0,02

0,025

0,03

0,035

32 31 20 35 22 11 17

lab code

exp

and

ed u

nce

rtai

nty

aclonifen - 1

-5

-4

-3

-2

-1

0

1

2

3

4

5

20 31 35 11 17 22 32

lab code

ζ-S

core

68,13

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,112 -0,8 s6 0,143 0,1 s8 0,138 0,0 s9 0,139 0,0 s

10 0,106 -0,9 s11 0,172 0,06 1,1 1,0 s13 0,096 -1,2 s15 0,13 -0,2 s17 0,147 0,078 0,2 0,3 s18 0,156 0,5 s20 0,095 0,03 -2,9 -1,2 s22 0,1348 0,04 -0,2 -0,1 s23 0,1218 -0,5 s29 0,143 0,1 s30 0,1483 0,3 s31 0,077 0,015 -8,1 -1,8 s32 0,238 0,001 147,9 2,9 q35 0,118 0,027 -1,5 -0,6 s36 0,167 0,8 s38 0,106 -0,9 s39 0,105 -1,0 s41 0,138 0,0 s

page C-4 of C-117



aclonifen - 20,13810,2072

0,06905

± 0,0009PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-5 of C-117

aclonifen - 2

0

0,05

0,1

0,15

0,2

0,2531 20 13 39 10 38 1 35 23 15 22 8 41 9 6 29 17 30 18 36 11 32

lab code

con

cen

trat

ion

in µ

g/l

aclonifen - 2

-3

-2

-1

0

1

2

3

4

31 20 13 39 10 38 1 35 23 15 22 8 41 9 6 29 17 30 18 36 11 32

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-6 of C-117

aclonifen - 2

0

0,01

0,02

0,03

0,04

0,05

0,06

0,07

0,08

0,09

32 31 35 20 22 11 17

lab code

exp

and

ed u

nce

rtai

nty

aclonifen - 2

-10

-8

-6

-4

-2

0

2

4

6

31 20 35 22 17 11 32

lab code

ζ-S

core

147,91

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,462 -0,8 s6 0,623 0,3 s8 0,602 0,1 s9 0,52 -0,4 s

10 0,328 -1,8 s11 0,4879 0,171 -1,1 -0,7 s13 0,46 -0,9 s15 0,505 -0,5 s17 0,711 0,137 1,8 0,9 s18 0,66 0,5 s20 0,385 0,12 -3,3 -1,4 s22 0,5722 0,172 -0,1 -0,1 s23 0,04724 -3,7 u29 0,62 0,2 s30 0,6444 0,4 s31 0,478 0,096 -2,2 -0,7 s32 0,632 0,001 24,0 0,3 s35 0,44 0,086 -3,4 -1,0 s36 0,727 1,0 s38 0,596 0,1 s39 0,4348 -1,0 s41 0,508 -0,5 s

page C-7 of C-117



aclonifen - 30,58450,87680,2923

± 0,0038PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-8 of C-117

aclonifen - 3

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

123 10 20 39 35 13 1 31 11 15 41 9 22 38 8 29 6 32 30 18 17 36

lab code

con

cen

trat

ion

in µ

g/l

aclonifen - 3

-4

-3

-2

-1

0

1

2

3

23 10 20 39 35 13 1 31 11 15 41 9 22 38 8 29 6 32 30 18 17 36

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-9 of C-117

aclonifen - 3

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,16

0,18

0,2

32 35 31 20 17 11 22

lab code

exp

and

ed u

nce

rtai

nty

aclonifen - 3

-5

0

5

10

15

20

25

30

35 20 31 11 22 17 32

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,099 1,7 s2 0,0876 0,009 4,0 1,0 s6 0,078 0,5 s7 0,09 0,03 1,4 1,2 s8 0,069 0,0 s9 0,066 -0,2 s

10 0,056 -0,8 s11 0,0694 0,028 0,0 0,0 s13 0,055 -0,8 s15 0,0736 0,2 s17 0,073 0,017 0,4 0,2 s18 0,071 0,1 s20 0,056 0,023 -1,2 -0,8 s22 0,0708 0,021 0,1 0,1 s23 0,06634 -0,2 s24 0,063 -0,4 s26 0,107 0,064 1,2 2,2 q27 0,068 0,034 -0,1 -0,1 s28 0,06998 0,0 s29 0,087 1,0 s30 0,07481 0,3 s31 0,076 0,015 0,9 0,4 s32 0,06 0,001 -17,1 -0,5 s35 0,069 0,013 -0,1 0,0 s36 0,077 0,4 s38 0,058 -0,7 s39 0,0645 -0,3 s41 0,0754 0,3 s42 0,069 0,03 0,0 0,0 s

page C-10 of C-117



alachlor - 10,06940,10410,0347

± 0,00046PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-11 of C-117

alachlor - 1

0

0,02

0,04

0,06

0,08

0,1

0,1213 10 20 38 32 24 39 9 23 27 8 35 42 11 28 22 18 17 15 30 41 31 36 6 29 2 7 1 26

lab code

con

cen

trat

ion

in µ

g/l

alachlor - 1

-2,5

-2

-1,5

-1

-0,5

0

0,5

1

1,5

2

2,5

13 10 20 38 32 24 39 9 23 27 8 35 42 11 28 22 18 17 15 30 41 31 36 6 29 2 7 1 26

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-12 of C-117

alachlor - 1

0

0,01

0,02

0,03

0,04

0,05

0,06

0,0732 2 35 31 17 22 20 11 7 42 27 26

lab code

exp

and

ed u

nce

rtai

nty

alachlor - 1

-20

-15

-10

-5

0

5

10

32 20 27 35 42 11 22 17 31 26 7 2

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,444 2,1 q2 0,3222 0,035 1,7 0,4 s6 0,325 0,4 s7 0,423 0,13 2,0 1,8 s8 0,298 0,1 s9 0,283 -0,1 s

10 0,231 -0,8 s11 0,2793 0,112 -0,2 -0,2 s13 0,25 -0,6 s15 0,276 -0,2 s17 0,338 0,029 3,1 0,6 s18 0,327 0,5 s20 0,229 0,096 -1,3 -0,9 s22 0,2853 0,086 -0,2 -0,1 s23 0,2741 -0,3 s24 0,264 -0,4 s26 0,464 0,23 1,5 2,3 q27 0,289 0,144 0,0 0,0 s28 0,2935 0,0 s29 0,335 0,6 s30 0,2912 0,0 s31 0,316 0,063 0,7 0,3 s32 0,25 0,001 -39,1 -0,6 s35 0,287 0,04 -0,3 -0,1 s36 0,373 1,1 s38 0,242 -0,7 s39 0,2178 -1,0 s41 0,3 0,1 s42 0,318 0,14 0,4 0,4 s

page C-13 of C-117



alachlor - 20,29240,43860,1462

± 0,0019PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-14 of C-117

alachlor - 2

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

0,45

0,539 20 10 38 13 32 24 23 15 11 9 22 35 27 30 28 8 41 31 42 2 6 18 29 17 36 7 1 26

lab code

con

cen

trat

ion

in µ

g/l

alachlor - 2

-2,5

-2

-1,5

-1

-0,5

0

0,5

1

1,5

2

2,5

3

39 20 10 38 13 32 24 23 15 11 9 22 35 27 30 28 8 41 31 42 2 6 18 29 17 36 7 1 26

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-15 of C-117

alachlor - 2

0

0,05

0,1

0,15

0,2

0,2532 17 2 35 31 22 20 11 7 42 27 26

lab code

exp

and

ed u

nce

rtai

nty

alachlor - 2

-5

-4

-3

-2

-1

0

1

2

3

4

32 20 35 11 22 27 42 31 26 2 7 17

lab code

ζ-S

core

-39,12

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,701 1,0 s2 0,8388 0,08 7,1 2,0 s6 0,613 0,4 s7 0,576 0,17 0,2 0,1 s8 0,536 -0,1 s9 0,518 -0,3 s

10 0,397 -1,1 s11 0,5445 0,218 -0,1 -0,1 s13 0,49 -0,5 s15 0,545 -0,1 s17 0,641 0,03 5,7 0,6 s18 0,568 0,1 s20 0,418 0,175 -1,6 -1,0 s22 0,5447 0,163 -0,1 -0,1 s23 0,8276 2,0 s24 0,5005 -0,4 s26 0,911 0,41 1,7 2,6 q27 0,505 0,253 -0,4 -0,4 s28 0,5713 0,1 s29 0,596 0,3 s30 0,5535 0,0 s31 0,609 0,122 0,9 0,4 s32 0,468 0,001 -46,1 -0,6 s35 0,544 0,07 -0,3 -0,1 s36 0,574 0,1 s38 0,467 -0,6 s39 0,4138 -1,0 s41 0,497 -0,4 s42 0,634 0,279 0,6 0,6 s

page C-16 of C-117



alachlor - 30,55530,833

0,2777

± 0,0036PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-17 of C-117

alachlor - 3

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

110 39 20 38 32 13 41 24 27 9 8 35 11 22 15 30 18 28 36 7 29 31 6 42 17 1 23 2 26

lab code

con

cen

trat

ion

in µ

g/l

alachlor - 3

-3

-2

-1

0

1

2

3

10 39 20 38 32 13 41 24 27 9 8 35 11 22 15 30 18 28 36 7 29 31 6 42 17 1 23 2 26

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-18 of C-117

alachlor - 3

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

0,4532 17 35 2 31 22 7 20 11 27 42 26

lab code

exp

and

ed u

nce

rtai

nty

alachlor - 3

-6

-4

-2

0

2

4

6

8

32 20 27 35 22 11 7 42 31 26 17 2

lab code

ζ-S

core

-46,14

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,133 2,8 q2 0,09311 0,007 4,0 0,8 s4 0,067 0,01 -2,2 -0,6 s6 0,084 0,3 s7 0,057 0,017 -2,5 -1,1 s8 0,076 -0,1 s9 0,066 -0,6 s

10 0,096 0,9 s11 0,0676 0,03 -0,7 -0,5 s13 0,045 -1,7 s15 0,0737 -0,2 s17 0,0821 0,013 0,6 0,2 s18 0,075 -0,2 s19 0,07 -0,4 s20 0,052 0,018 -2,9 -1,3 s22 0,07844 0,024 0,0 0,0 s23 0,05493 -1,2 s24 0,077 -0,1 s26 0,109 0,02 3,1 1,6 s27 0,076 0,019 -0,2 -0,1 s28 0,0601 -0,9 s29 0,093 0,8 s30 0,07645 -0,1 s31 0,081 0,016 0,4 0,1 s32 0,066 0,001 -21,5 -0,6 s35 0,072 0,015 -0,8 -0,3 s36 0,026 -2,7 q37 0,1775 5,1 u38 0,084 0,3 s39 0,0665 -0,6 s41 0,0732 -0,3 s42 0,097 0,043 0,9 1,0 s

page C-19 of C-117



atrazine - 10,07810,1172

0,03905

± 0,00052PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-20 of C-117

atrazine - 1

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,16

0,18

0,236 13 20 23 7 28 9 32 39 4 11 19 35 41 15 18 8 27 30 24 22 31 17 6 38 29 2 10 42 26 1 37

lab code

con

cen

trat

ion

in µ

g/l

atrazine - 1

-4

-3

-2

-1

0

1

2

3

4

5

6

36 13 20 23 7 28 9 32 39 4 11 19 35 41 15 18 8 27 30 24 22 31 17 6 38 29 2 10 42 26 1 37

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-21 of C-117

atrazine - 1

0

0,005

0,01

0,015

0,02

0,025

0,03

0,035

0,04

0,045

0,0532 2 4 17 35 31 7 20 27 26 22 11 42

lab code

exp

and

ed u

nce

rtai

nty

atrazine - 1

-25

-20

-15

-10

-5

0

5

10

32 20 7 4 35 11 27 22 31 17 42 26 2

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,071 -3,2 u2 0,4502 0,036 5,1 1,0 s4 0,337 0,051 -0,8 -0,2 s6 0,377 0,2 s7 0,271 0,081 -2,2 -1,0 s8 0,342 -0,2 s9 0,327 -0,3 s

10 0,4 0,5 s11 0,3208 0,144 -0,5 -0,4 s13 0,21 -1,7 s15 0,347 -0,1 s17 0,373 0,047 0,6 0,2 s18 0,311 -0,5 s19 0,3025 -0,6 s20 0,228 0,079 -3,3 -1,5 s22 0,369 0,111 0,2 0,1 s23 0,1981 -1,8 s24 0,3405 -0,2 s26 0,499 0,09 3,1 1,6 s27 0,287 0,072 -2,0 -0,8 s28 0,2785 -0,9 s29 0,359 0,0 s30 0,3779 0,2 s31 0,365 0,073 0,2 0,1 s32 0,289 0,001 -53,9 -0,8 s35 0,335 0,038 -1,2 -0,3 s36 0,114 -2,7 q37 0,5498 2,1 q38 0,35 -0,1 s39 0,3774 0,2 s41 0,324 -0,4 s42 0,596 0,262 1,8 2,7 q

page C-22 of C-117



atrazine - 20,35830,53750,1792

± 0,0024PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-23 of C-117

atrazine - 2

0

0,1

0,2

0,3

0,4

0,5

0,6

0,71 36 23 13 20 7 28 27 32 19 18 11 41 9 35 4 24 8 15 38 29 31 22 17 6 39 30 10 2 26 37 42

lab code

con

cen

trat

ion

in µ

g/l

atrazine - 2

-4

-3

-2

-1

0

1

2

3

1 36 23 13 20 7 28 27 32 19 18 11 41 9 35 4 24 8 15 38 29 31 22 17 6 39 30 10 2 26 37 42

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-24 of C-117

atrazine - 2

0

0,05

0,1

0,15

0,2

0,25

0,332 2 35 17 4 27 31 20 7 26 22 11 42

lab code

exp

and

ed u

nce

rtai

nty

atrazine - 2

-6

-4

-2

0

2

4

6

32 20 7 27 35 4 11 31 22 17 42 26 2

lab code

ζ-S

core

-53,91

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,524 -0,6 s2 0,6048 0,049 -0,4 -0,1 s4 0,557 0,084 -1,4 -0,4 s6 0,647 0,2 s7 0,477 0,14 -2,0 -0,9 s8 0,571 -0,3 s9 0,547 -0,4 s

10 0,732 0,8 s11 0,534 0,24 -0,7 -0,5 s13 0,35 -1,7 s15 0,568 -0,3 s17 0,646 0,068 0,9 0,2 s18 0,591 -0,2 s19 0,5438 -0,5 s20 0,39 0,135 -3,3 -1,5 s22 0,6588 0,198 0,4 0,3 s23 0,3566 -1,7 s24 0,556 -0,4 s26 0,769 0,14 2,2 1,0 s27 0,399 0,1 -4,3 -1,4 s28 0,4375 -1,2 s29 0,633 0,1 s30 0,6034 -0,1 s31 0,618 0,124 0,0 0,0 s32 0,505 0,001 -52,6 -0,7 s35 0,56 0,063 -1,7 -0,4 s36 0,184 -2,8 q37 0,8241 1,4 s38 0,584 -0,2 s39 0,564 -0,3 s41 0,517 -0,6 s42 0,52 0,229 -0,8 -0,6 s

page C-25 of C-117



atrazine - 30,61510,92270,3076

± 0,0041PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-26 of C-117

atrazine - 3

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

136 13 23 20 27 28 7 32 41 42 1 11 19 9 24 4 35 39 15 8 38 18 30 2 31 29 17 6 22 10 26 37

lab code

con

cen

trat

ion

in µ

g/l

atrazine - 3

-4

-3

-2

-1

0

1

2

3

36 13 23 20 27 28 7 32 41 42 1 11 19 9 24 4 35 39 15 8 38 18 30 2 31 29 17 6 22 10 26 37

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-27 of C-117

atrazine - 3

0

0,05

0,1

0,15

0,2

0,25

0,332 2 35 17 4 27 31 20 7 26 22 42 11

lab code

exp

and

ed u

nce

rtai

nty

atrazine - 3

-5

-4

-3

-2

-1

0

1

2

3

32 27 20 7 35 4 42 11 2 31 22 17 26

lab code

ζ-S

core

-52,64

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,059 -0,7 s2 0,01 -3,4 u6 0,074 0,1 s8 0,059 -0,7 s9 0,054 -1,0 s

10 0,061 -0,6 s11 0,0504 -1,2 s13 0,05 -1,2 s15 0,0526 -1,1 s17 0,0851 0,029 0,9 0,7 s18 0,036 -2,0 s20 0,053 0,022 -1,8 -1,1 s22 0,06678 0,02 -0,6 -0,3 s23 0,03146 -2,3 q29 0,051 -1,2 s30 0,06558 -0,4 s31 0,061 0,012 -1,9 -0,6 s32 0,039 0,001 -60,0 -1,8 s35 0,063 0,022 -0,8 -0,5 s36 0,127 3,0 u38 0,049 -1,3 s39 0,0418 -1,7 s41 0,0553 -0,9 s

page C-28 of C-117



bifenox - 10,07230,1085

0,03615

± 0,00048PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-29 of C-117

bifenox - 1

0

0,02

0,04

0,06

0,08

0,1

0,12

0,142 23 18 32 39 38 13 11 29 15 20 9 41 1 8 10 31 35 30 22 6 17 36

lab code

con

cen

trat

ion

in µ

g/l

bifenox - 1

-4

-3

-2

-1

0

1

2

3

4

2 23 18 32 39 38 13 11 29 15 20 9 41 1 8 10 31 35 30 22 6 17 36

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-30 of C-117

bifenox - 1

0

0,005

0,01

0,015

0,02

0,025

0,03

0,035

32 31 22 20 35 17

lab code

exp

and

ed u

nce

rtai

nty

bifenox - 1

-3

-2

-1

0

1

2

3

32 31 20 35 22 17

lab code

ζ-S

core

-60

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,256 -0,7 s2 0,1678 0,041 -6,7 -1,8 s6 0,265 -0,5 s8 0,26 -0,6 s9 0,209 -1,3 s

10 0,292 -0,2 s11 0,1708 -1,8 s13 0,23 -1,0 s15 0,191 -1,5 s17 0,324 0,101 0,4 0,2 s18 0,182 -1,6 s20 0,199 0,084 -2,5 -1,4 s22 0,2396 0,072 -1,8 -0,9 s23 0,2162 -1,2 s29 0,326 0,3 s30 0,2457 -0,8 s31 0,205 0,041 -4,9 -1,3 s32 0,201 0,001 -93,5 -1,4 s35 0,25 0,054 -2,1 -0,7 s36 0,393 1,1 s38 0,193 -1,5 s39 0,2121 -1,2 s41 0,237 -0,9 s

page C-31 of C-117



bifenox - 20,3060,4590,153

± 0,002PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-32 of C-117

bifenox - 2

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

0,45

0,52 11 18 15 38 20 32 31 9 39 23 13 41 22 30 35 1 8 6 10 17 29 36

lab code

con

cen

trat

ion

in µ

g/l

bifenox - 2

-2,5

-2

-1,5

-1

-0,5

0

0,5

1

1,5

2

2,5

2 11 18 15 38 20 32 31 9 39 23 13 41 22 30 35 1 8 6 10 17 29 36

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-33 of C-117

bifenox - 2

0

0,02

0,04

0,06

0,08

0,1

0,12

32 31 2 35 22 20 17

lab code

exp

and

ed u

nce

rtai

nty

bifenox - 2

-7

-6

-5

-4

-3

-2

-1

0

1

2

3

32 2 31 20 35 22 17

lab code

ζ-S

core

-93,55

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,291 -1,7 s2 0,3305 0,081 -4,6 -1,4 s6 0,418 -0,8 s8 0,442 -0,6 s9 0,41 -0,8 s

10 0,497 -0,1 s11 0,2816 -1,8 s13 0,38 -1,1 s15 0,397 -0,9 s17 0,538 0,208 0,2 0,2 s18 0,295 -1,7 s20 0,355 0,149 -2,2 -1,2 s22 0,4546 0,136 -0,9 -0,5 s23 0,316 -1,5 s29 0,572 0,4 s30 0,4212 -0,7 s31 0,336 0,067 -5,3 -1,4 s32 0,344 0,001 -97,2 -1,3 s35 0,345 0,062 -5,5 -1,3 s36 0,443 -0,6 s38 0,269 -1,9 s39 0,3718 -1,1 s41 0,436 -0,6 s

page C-34 of C-117



bifenox - 30,51540,77310,2577

± 0,0034PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-35 of C-117

bifenox - 3

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,938 11 1 18 23 2 31 32 35 20 39 13 15 9 6 30 41 8 36 22 10 17 29

lab code

con

cen

trat

ion

in µ

g/l

bifenox - 3

-2,5

-2

-1,5

-1

-0,5

0

0,5

1

1,5

2

2,5

38 11 1 18 23 2 31 32 35 20 39 13 15 9 6 30 41 8 36 22 10 17 29

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-36 of C-117

bifenox - 3

0

0,05

0,1

0,15

0,2

0,25

32 35 31 2 22 20 17

lab code

exp

and

ed u

nce

rtai

nty

bifenox - 3

-6

-5

-4

-3

-2

-1

0

1

2

3

32 35 31 2 20 22 17

lab code

ζ-S

core

-97,21

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,07 0,4 s2 0,07511 0,01 2,3 0,7 s6 0,066 0,2 s8 0,061 -0,2 s9 0,054 -0,6 s

10 0,036 -1,7 s11 0,0709 0,032 0,5 0,5 s13 0,06 -0,2 s15 0,0616 -0,1 s17 0,0967 0,02 3,3 2,1 q18 0,081 1,1 s20 0,057 0,018 -0,7 -0,4 s22 0,06685 0,021 0,3 0,2 s23 0,05248 -0,7 s24 0,0815 1,1 s26 0,079 0,052 0,6 1,0 s29 0,1 2,3 q30 0,07585 0,8 s31 0,064 0,013 0,1 0,0 s32 0,056 0,001 -12,1 -0,5 s35 0,063 0,012 -0,1 0,0 s36 0,167 6,5 u38 0,059 -0,3 s39 0,0788 1,0 s41 0,0673 0,2 s42 0,061 0,027 -0,2 -0,2 s

page C-37 of C-117



chlorfenvinphos - 10,0635

0,095250,03175

± 0,00073PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-38 of C-117

chlorfenvinphos - 1

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,16

0,1810 23 9 32 20 38 13 8 42 15 35 31 6 22 41 1 11 2 30 39 26 18 24 17 29 36

lab code

con

cen

trat

ion

in µ

g/l

chlorfenvinphos - 1

-3

-2

-1

0

1

2

3

4

5

6

7

10 23 9 32 20 38 13 8 42 15 35 31 6 22 41 1 11 2 30 39 26 18 24 17 29 36

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-39 of C-117

chlorfenvinphos - 1

0

0,01

0,02

0,03

0,04

0,05

0,0632 2 35 31 20 17 22 42 11 26

lab code

exp

and

ed u

nce

rtai

nty

chlorfenvinphos - 1

-14

-12

-10

-8

-6

-4

-2

0

2

4

6

32 20 42 35 31 22 11 26 2 17

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,15 0,4 s2 0,05496 0,014 -11,9 -2,4 q6 0,149 0,4 s8 0,128 -0,2 s9 0,115 -0,6 s

10 0,068 -2,0 s11 0,1535 0,069 0,5 0,5 s13 0,14 0,1 s15 0,133 -0,1 s17 0,211 0,05 3,0 2,2 q18 0,163 0,8 s20 0,106 0,033 -1,8 -0,9 s22 0,1403 0,042 0,2 0,1 s23 0,1258 -0,3 s24 0,1825 1,4 s26 0,171 0,1 0,7 1,0 s29 0,206 2,1 q30 0,1537 0,5 s31 0,145 0,029 0,6 0,3 s32 0,12 0,001 -17,4 -0,5 s35 0,127 0,014 -1,3 -0,3 s36 0,161 0,7 s38 0,126 -0,3 s39 0,1592 0,7 s41 0,147 0,3 s42 0,141 0,062 0,2 0,1 s

page C-40 of C-117



chlorfenvinphos - 20,1360,2040,068

± 0,0015PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-41 of C-117

chlorfenvinphos - 2

0

0,05

0,1

0,15

0,2

0,252 10 20 9 32 23 38 35 8 15 13 22 42 31 41 6 1 11 30 39 36 18 26 24 29 17

lab code

con

cen

trat

ion

in µ

g/l

chlorfenvinphos - 2

-3

-2

-1

0

1

2

3

2 10 20 9 32 23 38 35 8 15 13 22 42 31 41 6 1 11 30 39 36 18 26 24 29 17

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-42 of C-117

chlorfenvinphos - 2

0

0,02

0,04

0,06

0,08

0,1

0,1232 2 35 31 20 22 17 42 11 26

lab code

exp

and

ed u

nce

rtai

nty

chlorfenvinphos - 2

-20

-15

-10

-5

0

5

32 2 20 35 42 22 11 31 26 17

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,534 0,5 s2 0,1081 0,016 -43,5 -3,1 u6 0,499 0,2 s8 0,45 -0,2 s9 0,392 -0,7 s

10 0,251 -1,9 s11 0,4414 0,199 -0,3 -0,3 s13 0,51 0,3 s15 0,433 -0,4 s17 0,586 0,097 2,3 0,9 s18 0,591 1,0 s20 0,386 0,119 -1,5 -0,7 s22 0,5003 0,15 0,3 0,2 s23 0,4362 -0,3 s24 0,539 0,5 s26 0,545 0,27 0,5 0,6 s29 0,621 1,2 s30 0,498 0,2 s31 0,461 0,092 -0,3 -0,1 s32 0,431 0,001 -16,0 -0,4 s35 0,455 0,05 -0,8 -0,2 s36 0,478 0,0 s38 0,461 -0,1 s39 0,4489 -0,2 s41 0,468 -0,1 s42 0,483 0,213 0,1 0,1 s

page C-43 of C-117



chlorfenvinphos - 30,475

0,71250,2375

± 0,0054PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-44 of C-117

chlorfenvinphos - 3

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,82 10 20 9 32 15 23 11 39 8 35 31 38 41 36 42 30 6 22 13 1 24 26 17 18 29

lab code

con

cen

trat

ion

in µ

g/l

chlorfenvinphos - 3

-4

-3

-2

-1

0

1

2

3

2 10 20 9 32 15 23 11 39 8 35 31 38 41 36 42 30 6 22 13 1 24 26 17 18 29

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-45 of C-117

chlorfenvinphos - 3

0

0,05

0,1

0,15

0,2

0,25

0,332 2 35 31 17 20 22 11 42 26

lab code

exp

and

ed u

nce

rtai

nty

chlorfenvinphos - 3

-50

-40

-30

-20

-10

0

10

2 32 20 35 11 31 42 22 26 17

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,194 8,8 u2 0,02934 0,005 -12,0 -2,1 q6 0,085 1,6 s8 0,056 -0,3 s9 0,058 -0,2 s

10 0,045 -1,0 s11 0,0695 0,021 0,9 0,6 s13 0,04 -1,4 s15 0,0584 -0,1 s17 0,0744 0,014 2,0 0,9 s18 0,128 4,4 u20 0,056 0,018 -0,5 -0,3 s22 0,0806 0,024 1,7 1,3 s23 0,0633 0,2 s26 0,083 0,02 2,2 1,5 s29 0,102 2,7 q30 0,08595 1,7 s31 0,068 0,014 1,1 0,5 s32 0,052 0,001 -15,9 -0,6 s35 0,053 0,011 -1,4 -0,5 s36 0,076 1,0 s38 0,054 -0,4 s39 0,0422 -1,2 s41 0,0717 0,7 s42 0,061 0,027 0,0 0,0 s

page C-46 of C-117



chlorpyrifos-ethyl - 10,06060,09090,0303

± 0,00041PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-47 of C-117

chlorpyrifos-ethyl - 1

0

0,05

0,1

0,15

0,2

0,252 13 39 10 32 35 38 8 20 9 15 42 23 31 11 41 17 36 22 26 6 30 29 18 1

lab code

con

cen

trat

ion

in µ

g/l


-4

-2

0

2

4

6

8

10

2 13 39 10 32 35 38 8 20 9 15 42 23 31 11 41 17 36 22 26 6 30 29 18 1

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-48 of C-117


0

0,005

0,01

0,015

0,02

0,025

0,03

32 2 35 17 31 20 26 11 22 42

lab code

exp

and

ed u

nce

rtai

nty


-18

-16

-14

-12

-10

-8

-6

-4

-2

0

2

4

32 2 35 20 42 11 31 22 17 26

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,769 4,9 u2 0,1078 0,019 -24,4 -2,8 q6 0,474 1,5 s8 0,309 -0,4 s9 0,347 0,0 s

10 0,24 -1,2 s11 0,4315 0,129 1,3 1,0 s13 0,23 -1,3 s15 0,312 -0,4 s17 0,409 0,064 2,0 0,7 s18 0,641 3,4 u20 0,235 0,077 -2,9 -1,3 s22 0,4147 0,124 1,1 0,8 s23 0,2451 -1,2 s26 0,394 0,08 1,2 0,6 s29 0,443 1,1 s30 0,3694 0,3 s31 0,382 0,09 0,8 0,4 s32 0,277 0,001 -55,6 -0,8 s35 0,266 0,042 -3,8 -0,9 s36 0,371 0,3 s37 0,6075 3,0 u38 0,335 -0,1 s39 0,2565 -1,0 s41 0,382 0,4 s42 0,334 0,147 -0,2 -0,1 s

page C-49 of C-117




± 0,0023PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-50 of C-117


0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,92 13 20 10 23 39 35 32 8 15 42 38 9 30 36 31 41 26 17 22 11 29 6 37 18 1

lab code

con

cen

trat

ion

in µ

g/l


-4

-3

-2

-1

0

1

2

3

4

5

6

2 13 20 10 23 39 35 32 8 15 42 38 9 30 36 31 41 26 17 22 11 29 6 37 18 1

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-51 of C-117


0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,1632 2 35 17 20 26 31 22 11 42

lab code

exp

and

ed u

nce

rtai

nty


-60

-50

-40

-30

-20

-10

0

10

32 2 35 20 42 31 22 26 11 17

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 1,31 4,8 u2 0,1116 0,019 -49,4 -3,2 u6 0,904 2,1 q8 0,521 -0,5 s9 0,531 -0,4 s

10 0,347 -1,7 s11 0,71 0,213 1,1 0,8 s13 0,4 -1,3 s15 0,534 -0,4 s17 0,692 0,084 2,3 0,7 s18 0,92 2,2 q20 0,411 0,135 -2,7 -1,2 s22 0,6961 0,209 1,0 0,7 s23 0,3133 -1,9 s26 0,814 0,17 2,6 1,5 s29 0,71 0,8 s30 0,6168 0,1 s31 0,671 0,134 1,1 0,5 s32 0,46 0,001 -66,7 -0,9 s35 0,458 0,072 -3,8 -0,9 s36 0,609 0,1 s37 1,059 3,1 u38 0,543 -0,3 s39 0,3854 -1,4 s41 0,572 -0,2 s42 0,596 0,262 0,0 0,0 s

page C-52 of C-117




± 0,0039PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-53 of C-117


0

0,2

0,4

0,6

0,8

1

1,2

1,42 23 10 39 13 20 35 32 8 9 15 38 41 42 36 30 31 17 22 11 29 26 6 18 37 1

lab code

con

cen

trat

ion

in µ

g/l


-4

-3

-2

-1

0

1

2

3

4

5

6

2 23 10 39 13 20 35 32 8 9 15 38 41 42 36 30 31 17 22 11 29 26 6 18 37 1

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-54 of C-117


0

0,05

0,1

0,15

0,2

0,25

0,332 2 35 17 31 20 26 22 11 42

lab code

exp

and

ed u

nce

rtai

nty


-80

-70

-60

-50

-40

-30

-20

-10

0

10

32 2 35 20 42 22 11 31 17 26

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,048 -1,6 s4 0,078 0,016 -0,4 -0,1 s6 0,089 0,4 s7 0,065 0,02 -1,6 -0,8 s8 0,09 0,4 s9 0,062 -0,9 s

10 0,081 0,0 s11 0,1391 0,063 1,9 2,9 q13 0,07 -0,5 s15 0,0808 0,0 s17 0,101 0,018 2,2 1,0 s18 0,08 0,0 s19 0,0847 0,2 s20 0,069 0,015 -1,6 -0,6 s22 0,08259 0,025 0,1 0,1 s23 0,1023 1,1 s24 0,0895 0,4 s27 0,055 0,014 -3,7 -1,3 s28 0,06465 -0,8 s29 0,093 0,6 s30 0,08094 0,0 s31 0,089 0,018 0,9 0,4 s32 0,167 4,2 u35 0,077 0,017 -0,5 -0,2 s37 0,1101 1,4 s38 0,073 -0,4 s39 0,0728 -0,4 s41 0,0788 -0,1 s

page C-55 of C-117



diuron - 10,081

0,12150,0405

± 0,00054PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-56 of C-117

diuron - 1

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,16

0,181 27 9 28 7 20 13 39 38 35 4 41 18 15 30 10 22 19 6 31 24 8 29 17 23 37 11 32

lab code

con

cen

trat

ion

in µ

g/l

diuron - 1

-3

-2

-1

0

1

2

3

4

5

1 27 9 28 7 20 13 39 38 35 4 41 18 15 30 10 22 19 6 31 24 8 29 17 23 37 11 32

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-57 of C-117

diuron - 1

0

0,01

0,02

0,03

0,04

0,05

0,06

0,0727 20 4 35 17 31 7 22 11

lab code

exp

and

ed u

nce

rtai

nty

diuron - 1

-5

-4

-3

-2

-1

0

1

2

3

27 7 20 35 4 22 31 11 17

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,257 1,2 s4 0,205 0,041 0,4 0,2 s6 0,216 0,4 s7 0,145 0,043 -2,4 -1,0 s8 0,204 0,2 s9 0,185 -0,2 s

10 0,217 0,4 s11 0,332 0,149 1,8 2,8 q13 0,16 -0,7 s15 0,199 0,1 s17 0,24 0,035 2,5 0,9 s18 0,178 -0,4 s19 0,1823 -0,3 s20 0,172 0,038 -1,3 -0,5 s22 0,2025 0,061 0,2 0,1 s23 0,1427 -1,1 s24 0,206 0,2 s27 0,126 0,032 -4,4 -1,4 s28 0,1795 -0,3 s29 0,212 0,3 s30 0,1922 -0,1 s31 0,205 0,041 0,4 0,2 s32 0,125 -1,5 s35 0,176 0,029 -1,4 -0,4 s37 0,2142 0,4 s38 0,192 -0,1 s39 0,1546 -0,8 s41 0,175 -0,4 s

page C-58 of C-117



diuron - 20,19620,29430,0981

± 0,0013PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-59 of C-117

diuron - 2

0

0,05

0,1

0,15

0,2

0,25

0,3

0,3532 27 23 7 39 13 20 41 35 18 28 19 9 38 30 15 22 8 4 31 24 29 37 6 10 17 1 11

lab code

con

cen

trat

ion

in µ

g/l

diuron - 2

-3

-2

-1

0

1

2

3

4

32 27 23 7 39 13 20 41 35 18 28 19 9 38 30 15 22 8 4 31 24 29 37 6 10 17 1 11

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-60 of C-117

diuron - 2

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,1635 27 17 20 4 31 7 22 11

lab code

exp

and

ed u

nce

rtai

nty

diuron - 2

-5

-4

-3

-2

-1

0

1

2

3

27 7 35 20 22 4 31 11 17

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,53 0,7 s4 0,455 0,091 0,0 0,0 s6 0,47 0,1 s7 0,332 0,1 -2,5 -1,1 s8 0,472 0,1 s9 0,397 -0,5 s

10 0,564 1,0 s11 0,6718 0,302 1,4 1,9 s13 0,38 -0,7 s15 0,435 -0,2 s17 0,539 0,042 4,0 0,7 s18 0,432 -0,2 s19 0,3905 -0,6 s20 0,376 0,083 -1,9 -0,7 s22 0,4692 0,141 0,2 0,1 s23 0,3497 -0,9 s24 0,446 -0,1 s27 0,278 0,069 -5,1 -1,6 s28 0,3885 -0,6 s29 0,489 0,3 s30 0,4708 0,1 s31 0,449 0,09 -0,1 -0,1 s32 0,242 -1,9 s35 0,42 0,083 -0,8 -0,3 s37 0,4094 -0,4 s38 0,448 -0,1 s39 0,359 -0,8 s41 0,483 0,2 s

page C-61 of C-117



diuron - 30,455

0,68250,2275

± 0,003PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-62 of C-117

diuron - 3

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,832 27 7 23 39 20 13 28 19 9 37 35 18 15 24 38 31 4 22 6 30 8 41 29 1 17 10 11

lab code

con

cen

trat

ion

in µ

g/l

diuron - 3

-2,5

-2

-1,5

-1

-0,5

0

0,5

1

1,5

2

2,5

32 27 7 23 39 20 13 28 19 9 37 35 18 15 24 38 31 4 22 6 30 8 41 29 1 17 10 11

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-63 of C-117

diuron - 3

0

0,05

0,1

0,15

0,2

0,25

0,3

0,3517 27 20 35 31 4 7 22 11

lab code

exp

and

ed u

nce

rtai

nty

diuron - 3

-6

-4

-2

0

2

4

6

27 7 20 35 31 4 22 11 17

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,085 0,4 s2 0,06903 0,008 -2,2 -0,4 s4 0,067 0,01 -2,0 -0,5 s6 0,082 0,2 s7 0,057 0,017 -2,4 -1,0 s8 0,079 0,1 s9 0,073 -0,2 s

10 0,106 1,5 s11 0,0648 0,016 -1,5 -0,6 s13 0,068 -0,5 s15 0,0743 -0,2 s17 0,0912 0,016 1,7 0,7 s18 0,082 0,2 s19 0,0638 -0,7 s20 0,064 0,018 -1,5 -0,7 s22 0,06762 0,02 -0,9 -0,5 s23 0,07177 -0,3 s24 0,0825 0,3 s27 0,111 0,028 2,4 1,8 s28 0,0672 -0,5 s29 0,076 -0,1 s30 0,07401 -0,2 s31 0,077 0,015 0,0 0,0 s32 0,229 7,9 u35 0,074 0,015 -0,4 -0,2 s37 0,05915 -0,9 s38 0,082 0,2 s39 0,0735 -0,2 s41 0,0696 -0,4 s

page C-64 of C-117



isoproturon - 10,07720,11580,0386

± 0,00052PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-65 of C-117

isoproturon - 1

0

0,05

0,1

0,15

0,2

0,257 37 19 20 11 4 28 22 13 2 41 23 9 39 35 30 15 29 31 8 6 18 38 24 1 17 10 27 32

lab code

con

cen

trat

ion

in µ

g/l

isoproturon - 1

-4

-2

0

2

4

6

8

10

7 37 19 20 11 4 28 22 13 2 41 23 9 39 35 30 15 29 31 8 6 18 38 24 1 17 10 27 32

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-66 of C-117

isoproturon - 1

0

0,005

0,01

0,015

0,02

0,025

0,03

2 4 31 35 17 11 7 20 22 27

lab code

exp

and

ed u

nce

rtai

nty

isoproturon - 1

-3

-2

-1

0

1

2

3

7 2 4 11 20 22 35 31 17 27

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,172 -1,4 s2 0,4521 0,049 7,5 2,7 q4 0,258 0,039 -0,5 -0,2 s6 0,269 0,0 s7 0,21 0,063 -1,9 -0,9 s8 0,272 0,1 s9 0,242 -0,4 s

10 0,283 0,2 s11 0,2404 0,06 -0,9 -0,4 s13 0,24 -0,4 s15 0,267 0,0 s17 0,317 0,029 3,3 0,7 s18 0,262 -0,1 s19 0,2705 0,0 s20 0,221 0,063 -1,5 -0,7 s22 0,2538 0,076 -0,4 -0,2 s23 0,3911 1,8 s24 0,282 0,2 s27 0,384 0,096 2,4 1,7 s28 0,23 -0,6 s29 0,272 0,1 s30 0,2903 0,3 s31 0,263 0,053 -0,2 -0,1 s32 0,348 1,2 s35 0,261 0,043 -0,3 -0,1 s37 0,2321 -0,5 s38 0,277 0,1 s39 0,2796 0,2 s41 0,254 -0,2 s

page C-67 of C-117



isoproturon - 20,26850,40280,1343

± 0,0018PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-68 of C-117

isoproturon - 2

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

0,45

0,51 7 20 28 37 13 11 9 22 41 4 35 18 31 15 6 19 8 29 38 39 24 10 30 17 32 27 23 2

lab code

con

cen

trat

ion

in µ

g/l

isoproturon - 2

-3

-2

-1

0

1

2

3

1 7 20 28 37 13 11 9 22 41 4 35 18 31 15 6 19 8 29 38 39 24 10 30 17 32 27 23 2

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-69 of C-117

isoproturon - 2

0

0,02

0,04

0,06

0,08

0,1

0,1217 4 35 2 31 11 7 20 22 27

lab code

exp

and

ed u

nce

rtai

nty

isoproturon - 2

-4

-2

0

2

4

6

8

7 20 11 4 22 35 31 27 17 2

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,462 -0,7 s2 0,7937 0,087 5,4 1,7 s4 0,542 0,081 -0,4 -0,1 s6 0,546 -0,1 s7 0,44 0,13 -1,8 -0,9 s8 0,572 0,1 s9 0,484 -0,5 s

10 0,54 -0,1 s11 0,4948 0,124 -1,0 -0,5 s13 0,48 -0,6 s15 0,507 -0,4 s17 0,652 0,094 2,0 0,7 s18 0,592 0,2 s19 0,531 -0,2 s20 0,426 0,121 -2,2 -1,0 s22 0,5408 0,162 -0,2 -0,1 s23 0,8618 2,2 q24 0,5235 -0,3 s27 0,811 0,203 2,5 1,8 s28 0,4465 -0,8 s29 0,558 0,0 s30 0,5587 0,0 s31 0,552 0,11 -0,1 -0,1 s32 0,506 -0,4 s35 0,542 0,084 -0,4 -0,1 s37 0,4181 -1,0 s38 0,535 -0,2 s39 0,5773 0,1 s41 0,503 -0,4 s

page C-70 of C-117



isoproturon - 30,55960,83940,2798

± 0,0037PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-71 of C-117

isoproturon - 3

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

137 20 7 28 1 13 9 11 41 32 15 24 19 38 10 22 4 35 6 31 29 30 8 39 18 17 2 27 23

lab code

con

cen

trat

ion

in µ

g/l

isoproturon - 3

-2,5

-2

-1,5

-1

-0,5

0

0,5

1

1,5

2

2,5

37 20 7 28 1 13 9 11 41 32 15 24 19 38 10 22 4 35 6 31 29 30 8 39 18 17 2 27 23

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-72 of C-117

isoproturon - 3

0

0,05

0,1

0,15

0,2

0,254 35 2 17 31 20 11 7 22 27

lab code

exp

and

ed u

nce

rtai

nty

isoproturon - 3

-3

-2

-1

0

1

2

3

4

5

6

20 7 11 4 35 22 31 17 27 2

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,065 0,1 s2 0,01 -3,4 u6 0,067 0,2 s8 0,055 -0,5 s9 0,063 0,0 s

10 0,048 -1,0 s11 0,075 0,026 0,9 0,7 s15 0,0446 -1,2 s17 0,0835 0,014 2,9 1,3 s18 0,109 2,9 q22 0,07964 0,024 1,4 1,0 s23 0,05408 -0,6 s29 0,08 1,0 s30 0,09194 1,8 s31 0,074 0,015 1,4 0,7 s32 0,051 0,001 -23,0 -0,8 s35 0,049 0,013 -2,2 -0,9 s36 0,097 2,1 q38 0,096 2,0 s39 0,1449 5,1 u41 0,0696 0,4 s

page C-73 of C-117



quinoxyfen - 10,0635

0,095250,03175

± 0,00043PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-74 of C-117

quinoxyfen - 1

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,162 15 10 35 32 23 8 9 1 6 41 31 11 22 29 17 30 38 36 18 39

lab code

con

cen

trat

ion

in µ

g/l

quinoxyfen - 1

-4

-3

-2

-1

0

1

2

3

4

5

6

2 15 10 35 32 23 8 9 1 6 41 31 11 22 29 17 30 38 36 18 39

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-75 of C-117

quinoxyfen - 1

0

0,005

0,01

0,015

0,02

0,025

0,03

32 35 17 31 22 11

lab code

exp

and

ed u

nce

rtai

nty

quinoxyfen - 1

-25

-20

-15

-10

-5

0

5

32 35 11 22 31 17

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,218 0,1 s2 0,108 0,017 -12,3 -2,0 s6 0,216 0,1 s8 0,185 -0,5 s9 0,16 -1,0 s

10 0,173 -0,7 s11 0,2629 0,092 1,1 0,9 s15 0,144 -1,3 s17 0,275 0,029 4,3 1,2 s18 0,371 3,0 u22 0,2668 0,08 1,4 1,0 s23 0,1645 -0,9 s29 0,271 1,1 s30 0,2843 1,4 s31 0,221 0,044 0,4 0,2 s32 0,179 0,001 -38,9 -0,6 s35 0,137 0,03 -5,0 -1,4 s36 0,242 0,6 s38 0,034 -3,4 u39 0,3479 2,5 q41 0,172 -0,8 s

page C-76 of C-117



quinoxyfen - 20,21250,31880,1063

± 0,0014PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-77 of C-117

quinoxyfen - 2

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,438 2 35 15 9 23 41 10 32 8 6 1 31 36 11 22 29 17 30 39 18

lab code

con

cen

trat

ion

in µ

g/l

quinoxyfen - 2

-4

-3

-2

-1

0

1

2

3

4

38 2 35 15 9 23 41 10 32 8 6 1 31 36 11 22 29 17 30 39 18

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-78 of C-117

quinoxyfen - 2

0

0,01

0,02

0,03

0,04

0,05

0,06

0,07

0,08

0,09

0,1

32 2 17 35 31 22 11

lab code

exp

and

ed u

nce

rtai

nty

quinoxyfen - 2

-45

-40

-35

-30

-25

-20

-15

-10

-5

0

5

10

32 2 35 31 11 22 17

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,464 -0,6 s2 0,2683 0,042 -13,5 -2,1 q6 0,54 -0,1 s8 0,497 -0,4 s9 0,386 -1,2 s

10 0,4 -1,1 s11 0,743 0,26 1,5 1,4 s15 0,366 -1,4 s17 0,686 0,09 2,9 1,0 s18 0,978 3,1 u22 0,6741 0,202 1,2 0,9 s23 0,4696 -0,6 s29 0,545 -0,1 s30 0,7201 1,2 s31 0,532 0,106 -0,4 -0,2 s32 0,456 0,001 -51,6 -0,7 s35 0,429 0,102 -2,4 -0,9 s36 0,559 0,0 s38 0,157 -2,9 q39 0,853 2,2 q41 0,486 -0,5 s

page C-79 of C-117



quinoxyfen - 30,55340,83010,2767

± 0,0036PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-80 of C-117

quinoxyfen - 3

0

0,2

0,4

0,6

0,8

1

1,238 2 15 9 10 35 32 1 23 41 8 31 6 29 36 22 17 30 11 39 18

lab code

con

cen

trat

ion

in µ

g/l

quinoxyfen - 3

-4

-3

-2

-1

0

1

2

3

4

38 2 15 9 10 35 32 1 23 41 8 31 6 29 36 22 17 30 11 39 18

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-81 of C-117

quinoxyfen - 3

0

0,05

0,1

0,15

0,2

0,25

0,3

32 2 17 35 31 22 11

lab code

exp

and

ed u

nce

rtai

nty

quinoxyfen - 3

-60

-50

-40

-30

-20

-10

0

10

32 2 35 31 22 11 17

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,071 0,0 s2 0,09448 0,009 5,6 1,4 s4 0,062 0,009 -1,8 -0,5 s6 0,075 0,3 s7 0,062 0,019 -0,9 -0,5 s8 0,074 0,2 s9 0,075 0,3 s

10 0,086 0,9 s11 0,06 0,018 -1,2 -0,6 s13 0,04 -1,7 s15 0,0711 0,0 s17 0,0804 0,013 1,5 0,6 s18 0,065 -0,3 s19 0,043 -1,6 s20 0,054 0,012 -2,7 -0,9 s22 0,0681 0,02 -0,2 -0,1 s23 0,05185 -1,1 s24 0,076 0,3 s26 0,107 0,02 3,7 2,1 q27 0,141 0,035 4,0 4,0 u28 0,0627 -0,4 s29 0,078 0,4 s30 0,07387 0,2 s31 0,058 0,012 -2,1 -0,7 s32 0,058 0,001 -22,4 -0,7 s35 0,069 0,014 -0,2 -0,1 s36 0,025 -2,6 q37 0,1694 5,6 u38 0,071 0,0 s39 1,258 67,5 u41 0,0655 -0,3 s42 0,046 0,02 -2,4 -1,4 s

page C-82 of C-117



simazine - 10,07040,10560,0352

± 0,00047PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-83 of C-117

simazine - 1

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,16

0,18

0,236 13 19 42 23 20 31 32 11 4 7 28 18 41 22 35 1 38 15 30 8 6 9 24 29 17 10 2 26 27 37 39

lab code

con

cen

trat

ion

in µ

g/l

1,258

simazine - 1

-4

-3

-2

-1

0

1

2

3

4

5

6

36 13 19 42 23 20 31 32 11 4 7 28 18 41 22 35 1 38 15 30 8 6 9 24 29 17 10 2 26 27 37 39

lab code

z-sc

ore

67,48

PT 5/11 - PT-WFD

page C-84 of C-117

simazine - 1

0

0,005

0,01

0,015

0,02

0,025

0,03

0,035

0,0432 2 4 20 31 17 35 11 7 26 42 22 27

lab code

exp

and

ed u

nce

rtai

nty

simazine - 1

-25

-20

-15

-10

-5

0

5

10

32 20 42 31 4 11 7 22 35 17 26 27 2

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,335 -0,2 s2 0,3516 0,032 0,1 0,0 s4 0,329 0,049 -0,8 -0,2 s6 0,359 0,1 s7 0,3 0,09 -1,1 -0,6 s8 0,346 0,0 s9 0,333 -0,2 s

10 0,366 0,2 s11 0,3298 0,099 -0,4 -0,2 s13 0,23 -1,4 s15 0,327 -0,3 s17 0,375 0,054 0,9 0,3 s18 0,342 -0,1 s19 0,2593 -1,0 s20 0,258 0,06 -3,1 -1,1 s22 0,3557 0,107 0,1 0,1 s23 0,238 -1,3 s24 0,332 -0,2 s26 0,476 0,08 3,1 1,4 s27 0,697 0,174 4,0 4,0 u28 0,291 -0,7 s29 0,35 0,0 s30 0,3621 0,1 s31 0,257 0,051 -3,6 -1,1 s32 0,293 0,001 -45,3 -0,7 s35 0,329 0,062 -0,7 -0,2 s36 0,06 -3,3 u37 0,5636 2,4 q38 0,328 -0,3 s39 6,127 66,0 u41 0,325 -0,3 s42 0,195 0,086 -3,6 -1,8 s

page C-85 of C-117



simazine - 20,35

0,5250,175

± 0,0023PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-86 of C-117

simazine - 2

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

136 42 13 23 31 20 19 28 32 7 41 15 38 4 35 11 24 9 1 18 8 29 2 22 6 30 10 17 26 37 27 39

lab code

con

cen

trat

ion

in µ

g/l

6,127

simazine - 2

-4

-3

-2

-1

0

1

2

3

4

5

36 42 13 23 31 20 19 28 32 7 41 15 38 4 35 11 24 9 1 18 8 29 2 22 6 30 10 17 26 37 27 39

lab code

z-sc

ore

66,02

PT 5/11 - PT-WFD

page C-87 of C-117

simazine - 2

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,16

0,18

0,232 2 4 31 17 20 35 26 42 7 11 22 27

lab code

exp

and

ed u

nce

rtai

nty

simazine - 2

-50

-40

-30

-20

-10

0

10

32 31 42 20 7 4 35 11 2 22 17 26 27

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,607 0,0 s2 0,643 0,059 1,0 0,2 s4 0,618 0,927 0,0 0,0 s6 0,637 0,1 s7 0,57 0,17 -0,5 -0,3 s8 0,589 -0,2 s9 0,524 -0,6 s

10 0,618 0,0 s11 0,5579 0,167 -0,7 -0,4 s13 0,38 -1,5 s15 0,558 -0,4 s17 0,649 0,103 0,7 0,2 s18 0,539 -0,5 s19 0,4409 -1,1 s20 0,448 0,103 -3,2 -1,1 s22 0,6344 0,19 0,2 0,1 s23 0,4764 -0,9 s24 0,5555 -0,4 s26 0,872 0,16 3,2 1,7 s27 1,162 0,29 3,8 3,6 u28 0,538 -0,5 s29 0,632 0,1 s30 0,625 0,1 s31 0,434 0,087 -4,1 -1,2 s32 0,501 0,001 -54,2 -0,7 s35 0,568 0,117 -0,8 -0,3 s36 0,06 -3,6 u37 0,9244 2,0 s38 0,577 -0,2 s39 12,21 75,5 u41 0,621 0,0 s42 0,367 0,161 -3,1 -1,6 s

page C-88 of C-117



simazine - 30,6140,9210,307

± 0,004PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-89 of C-117

simazine - 3

0

0,2

0,4

0,6

0,8

1

1,2

1,436 42 13 31 19 20 23 32 9 28 18 24 11 15 35 7 38 8 1 4 10 41 30 29 22 6 2 17 26 37 27 39

lab code

con

cen

trat

ion

in µ

g/l

12,21

simazine - 3

-5

-4

-3

-2

-1

0

1

2

3

4

5

36 42 13 31 19 20 23 32 9 28 18 24 11 15 35 7 38 8 1 4 10 41 30 29 22 6 2 17 26 37 27 39

lab code

z-sc

ore

75,54

PT 5/11 - PT-WFD

page C-90 of C-117

simazine - 3

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

132 2 31 17 20 35 26 42 11 7 22 27 4

lab code

exp

and

ed u

nce

rtai

nty

simazine - 3

-60

-50

-40

-30

-20

-10

0

10

32 31 20 42 35 11 7 4 22 17 2 26 27

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,066 0,2 s2 0,08098 0,006 6,1 1,2 s6 0,07 0,5 s7 0,059 0,018 -0,4 -0,2 s8 0,066 0,2 s9 0,069 0,4 s

10 0,067 0,3 s11 0,0635 0,025 0,1 0,1 s13 0,06 -0,1 s15 0,0626 0,0 s17 0,0812 0,015 2,5 1,2 s18 0,079 1,1 s20 0,047 0,008 -3,8 -1,0 s22 0,06285 0,019 0,1 0,0 s23 0,04889 -0,9 s24 0,067 0,3 s26 0,082 0,02 2,0 1,3 s27 0,109 0,055 1,7 3,0 u28 0,04545 -1,1 s29 0,059 -0,2 s30 0,06733 0,3 s31 0,063 0,013 0,1 0,1 s32 0,055 0,001 -13,3 -0,5 s35 0,063 0,013 0,1 0,1 s36 0,048 -0,9 s37 0,2883 14,5 u38 0,065 0,2 s39 0,0784 1,0 s41 0,0581 -0,3 s42 0,053 0,023 -0,8 -0,6 s

page C-91 of C-117



terbutryn - 10,06220,09330,0311

± 0,00042PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-92 of C-117

terbutryn - 1

0

0,05

0,1

0,15

0,2

0,25

0,3

0,3528 20 36 23 42 32 41 7 29 13 15 22 31 35 11 38 1 8 10 24 30 9 6 39 18 2 17 26 27 37

lab code

con

cen

trat

ion

in µ

g/l

terbutryn - 1

-4

-2

0

2

4

6

8

10

12

14

16

28 20 36 23 42 32 41 7 29 13 15 22 31 35 11 38 1 8 10 24 30 9 6 39 18 2 17 26 27 37

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-93 of C-117

terbutryn - 1

0

0,01

0,02

0,03

0,04

0,05

0,0632 2 20 31 35 17 7 22 26 42 11 27

lab code

exp

and

ed u

nce

rtai

nty

terbutryn - 1

-15

-10

-5

0

5

10

32 20 42 7 22 11 31 35 27 26 17 2

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,309 0,5 s2 0,3401 0,026 4,9 0,9 s6 0,291 0,2 s7 0,255 0,076 -0,6 -0,3 s8 0,27 -0,1 s9 0,252 -0,4 s

10 0,254 -0,3 s11 0,2622 0,105 -0,3 -0,2 s13 0,22 -0,8 s15 0,262 -0,2 s17 0,314 0,036 2,1 0,5 s18 0,311 0,5 s20 0,182 0,03 -6,3 -1,4 s22 0,2803 0,084 0,1 0,1 s23 0,2769 0,0 s24 0,2915 0,2 s26 0,372 0,098 1,9 1,4 s27 0,472 0,236 1,7 2,8 q28 0,194 -1,2 s29 0,256 -0,3 s30 0,313 0,5 s31 0,277 0,055 0,0 0,0 s32 0,24 0,001 -35,3 -0,5 s35 0,271 0,039 -0,3 -0,1 s36 0,058 -3,2 u37 0,4916 3,1 u38 0,271 -0,1 s39 0,2813 0,1 s41 0,26 -0,2 s42 0,256 0,113 -0,4 -0,3 s

page C-94 of C-117



terbutryn - 20,27660,41490,1383

± 0,0018PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-95 of C-117

terbutryn - 2

0

0,1

0,2

0,3

0,4

0,5

0,636 20 28 13 32 9 10 7 29 42 41 15 11 8 35 38 23 31 22 39 6 24 1 18 30 17 2 26 27 37

lab code

con

cen

trat

ion

in µ

g/l

terbutryn - 2

-4

-3

-2

-1

0

1

2

3

4

36 20 28 13 32 9 10 7 29 42 41 15 11 8 35 38 23 31 22 39 6 24 1 18 30 17 2 26 27 37

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-96 of C-117

terbutryn - 2

0

0,05

0,1

0,15

0,2

0,2532 2 20 17 35 31 7 22 26 11 42 27

lab code

exp

and

ed u

nce

rtai

nty

terbutryn - 2

-40

-35

-30

-25

-20

-15

-10

-5

0

5

10

32 20 7 42 35 11 31 22 27 26 17 2

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,476 -0,1 s2 0,6927 0,053 7,7 1,7 s6 0,5 0,1 s7 0,442 0,13 -0,7 -0,4 s8 0,459 -0,2 s9 0,441 -0,4 s

10 0,41 -0,6 s11 0,4628 0,185 -0,3 -0,2 s13 0,32 -1,4 s15 0,462 -0,2 s17 0,526 0,055 1,4 0,3 s18 0,491 0,0 s20 0,351 0,058 -4,7 -1,1 s22 0,4891 0,147 0,0 0,0 s23 0,6686 1,5 s24 0,5055 0,1 s26 0,675 0,18 2,1 1,5 s27 0,823 0,411 1,6 2,7 q28 0,3725 -1,0 s29 0,468 -0,2 s30 0,5202 0,3 s31 0,489 0,098 0,0 0,0 s32 0,41 0,001 -46,9 -0,6 s35 0,48 0,068 -0,3 -0,1 s36 0,192 -2,4 q37 0,7604 2,2 q38 0,515 0,2 s39 0,5251 0,3 s41 0,442 -0,4 s42 0,462 0,203 -0,3 -0,2 s

page C-97 of C-117



terbutryn - 30,48880,73320,2444

± 0,0032PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-98 of C-117

terbutryn - 3

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,936 13 20 28 10 32 9 7 41 8 15 42 11 29 1 35 31 22 18 6 24 38 30 39 17 23 26 2 37 27

lab code

con

cen

trat

ion

in µ

g/l

terbutryn - 3

-3

-2

-1

0

1

2

3

36 13 20 28 10 32 9 7 41 8 15 42 11 29 1 35 31 22 18 6 24 38 30 39 17 23 26 2 37 27

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-99 of C-117

terbutryn - 3

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,4

0,4532 2 17 20 35 31 7 22 26 11 42 27

lab code

exp

and

ed u

nce

rtai

nty

terbutryn - 3

-50

-40

-30

-20

-10

0

10

20

32 20 7 11 42 35 31 22 17 27 26 2

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,067 0,0 s6 0,058 -0,6 s8 0,08 0,7 s9 0,067 0,0 s

10 0,063 -0,3 s11 0,065 0,023 -0,2 -0,2 s15 0,0554 -0,7 s17 0,0464 0,008 -5,3 -1,3 s18 0,065 -0,2 s20 0,059 0,018 -1,0 -0,5 s22 0,06075 0,018 -0,8 -0,4 s23 0,05045 -1,0 s26 0,141 0,026 5,6 4,3 u29 0,054 -0,8 s30 0,06716 0,0 s31 0,116 0,023 4,2 2,8 q32 0,054 0,001 -25,2 -0,8 s35 0,087 0,016 2,4 1,1 s36 0,055 -0,8 s38 0,059 -0,5 s39 0,137 4,1 u41 0,0448 -1,4 s42 0,017 0,007 -14,5 -3,0 u

page C-100 of C-117



trifluralin - 10,06780,10170,0339

± 0,00045PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-101 of C-117

trifluralin - 1

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,1642 41 17 23 29 32 36 15 6 20 38 22 10 11 18 1 9 30 8 35 31 39 26

lab code

con

cen

trat

ion

in µ

g/l

trifluralin - 1

-4

-3

-2

-1

0

1

2

3

4

5

42 41 17 23 29 32 36 15 6 20 38 22 10 11 18 1 9 30 8 35 31 39 26

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-102 of C-117

trifluralin - 1

0

0,005

0,01

0,015

0,02

0,025

0,03

32 42 17 35 20 22 11 31 26

lab code

exp

and

ed u

nce

rtai

nty

trifluralin - 1

-30

-25

-20

-15

-10

-5

0

5

10

32 42 17 20 22 11 35 31 26

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,318 0,0 s6 0,247 -0,9 s8 0,328 0,1 s9 0,328 0,1 s

10 0,239 -1,0 s11 0,3098 0,108 -0,2 -0,1 s15 0,265 -0,7 s17 0,287 0,03 -2,1 -0,4 s18 0,247 -0,9 s20 0,279 0,084 -0,9 -0,5 s22 0,2613 0,078 -1,5 -0,7 s23 0,2042 -1,4 s26 0,943 0,18 6,9 7,8 u29 0,292 -0,3 s30 0,2893 -0,4 s31 0,485 0,097 3,4 2,1 q32 0,227 0,001 -79,3 -1,2 s35 0,374 0,06 1,8 0,7 s36 0,279 -0,5 s38 0,265 -0,7 s39 0,2157 -1,3 s41 0,18 -1,7 s42 0,068 0,03 -16,7 -3,1 u

page C-103 of C-117



trifluralin - 20,31890,47840,1595

± 0,0021PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-104 of C-117

trifluralin - 2

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

142 41 23 39 32 10 6 18 22 15 38 20 36 17 30 29 11 1 8 9 35 31 26

lab code

con

cen

trat

ion

in µ

g/l

trifluralin - 2

-4

-2

0

2

4

6

8

10

42 41 23 39 32 10 6 18 22 15 38 20 36 17 30 29 11 1 8 9 35 31 26

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-105 of C-117

trifluralin - 2

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,16

0,18

0,232 17 42 35 22 20 31 11 26

lab code

exp

and

ed u

nce

rtai

nty

trifluralin - 2

-90

-80

-70

-60

-50

-40

-30

-20

-10

0

10

20

32 42 17 22 20 11 35 31 26

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,524 -0,4 s6 0,469 -0,8 s8 0,596 0,1 s9 0,562 -0,1 s

10 0,453 -0,9 s11 0,5932 0,208 0,1 0,1 s15 0,418 -1,1 s17 0,427 0,085 -3,6 -1,1 s18 0,652 0,5 s20 0,472 0,143 -1,5 -0,8 s22 0,5347 0,16 -0,6 -0,3 s23 0,4133 -1,2 s26 0,998 0,19 4,4 2,9 q29 0,57 -0,1 s30 0,5282 -0,4 s31 0,909 0,182 3,6 2,2 q32 0,461 0,001 -61,5 -0,8 s35 0,597 0,086 0,3 0,1 s36 0,527 -0,4 s38 0,479 -0,7 s39 0,6242 0,3 s41 0,324 -1,8 s42 0,575 0,253 -0,1 0,0 s

page C-106 of C-117



trifluralin - 30,58210,87320,2911

± 0,0038PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-107 of C-117

trifluralin - 3

0

0,2

0,4

0,6

0,8

1

1,241 23 15 17 10 32 6 20 38 1 36 30 22 9 29 42 11 8 35 39 18 31 26

lab code

con

cen

trat

ion

in µ

g/l

trifluralin - 3

-3

-2

-1

0

1

2

3

4

41 23 15 17 10 32 6 20 38 1 36 30 22 9 29 42 11 8 35 39 18 31 26

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-108 of C-117

trifluralin - 3

0

0,05

0,1

0,15

0,2

0,25

0,332 17 35 20 22 31 26 11 42

lab code

exp

and

ed u

nce

rtai

nty

trifluralin - 3

-70

-60

-50

-40

-30

-20

-10

0

10

32 17 20 22 42 11 35 31 26

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,09 1,6 s2 0,07479 0,005 4,0 0,6 s4 0,068 0,01 0,6 0,2 s6 0,069 0,3 s8 0,067 0,1 s9 0,073 0,5 s

15 0,0665 0,1 s17 0,0691 0,012 0,7 0,3 s18 0,077 0,8 s20 0,047 0,02 -1,8 -1,1 s22 0,064 0,019 -0,1 0,0 s23 0,02755 -2,3 q24 0,0685 0,2 s27 0,029 0,014 -5,1 -2,2 q28 0,05365 -0,7 s29 0,07 0,3 s30 0,07632 0,7 s31 0,065 0,013 0,0 0,0 s32 0,06 0,001 -8,8 -0,3 s35 0,064 0,013 -0,1 0,0 s37 0,3361 16,7 u38 0,057 -0,5 s39 0,0644 0,0 s41 0,0634 -0,1 s

page C-109 of C-117



cybutryne - 10,06480,09720,0324

± 0,00043PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-110 of C-117

cybutryne - 1

0

0,05

0,1

0,15

0,2

0,25

0,3

0,35

0,423 27 20 28 38 32 41 22 35 39 31 15 8 4 24 6 17 29 9 2 30 18 1 37

lab code

con

cen

trat

ion

in µ

g/l

cybutryne - 1

-5

0

5

10

15

20

23 27 20 28 38 32 41 22 35 39 31 15 8 4 24 6 17 29 9 2 30 18 1 37

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-111 of C-117

cybutryne - 1

0

0,005

0,01

0,015

0,02

0,025

32 2 4 17 31 35 27 22 20

lab code

exp

and

ed u

nce

rtai

nty

cybutryne - 1

-10

-8

-6

-4

-2

0

2

4

6

32 27 20 35 22 31 4 17 2

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,286 0,1 s2 0,3772 0,025 7,9 1,4 s4 0,297 0,045 0,9 0,3 s6 0,307 0,4 s8 0,279 0,0 s9 0,235 -0,6 s

15 0,285 0,1 s17 0,299 0,037 1,2 0,3 s18 0,319 0,6 s20 0,198 0,081 -2,0 -1,1 s22 0,2915 0,087 0,3 0,2 s23 0,1199 -2,3 q24 0,2945 0,2 s27 0,065 0,032 -13,3 -3,1 u28 0,2205 -0,8 s29 0,3 0,3 s30 0,3402 0,9 s31 0,275 0,055 -0,1 0,0 s32 0,237 0,001 -38,9 -0,6 s35 0,262 0,033 -0,9 -0,2 s37 0,6719 5,7 u38 0,241 -0,5 s39 0,2971 0,3 s41 0,302 0,4 s

page C-112 of C-117



cybutryne - 20,27750,41630,1388

± 0,0018PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-113 of C-117

cybutryne - 2

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,827 23 20 28 9 32 38 35 31 8 15 1 22 24 4 39 17 29 41 6 18 30 2 37

lab code

con

cen

trat

ion

in µ

g/l

cybutryne - 2

-4

-3

-2

-1

0

1

2

3

4

5

6

7

27 23 20 28 9 32 38 35 31 8 15 1 22 24 4 39 17 29 41 6 18 30 2 37

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-114 of C-117

cybutryne - 2

0

0,01

0,02

0,03

0,04

0,05

0,06

0,07

0,08

0,09

0,132 2 27 35 17 4 31 20 22

lab code

exp

and

ed u

nce

rtai

nty

cybutryne - 2

-50

-40

-30

-20

-10

0

10

20

32 27 20 35 31 22 4 17 2

lab code

ζ-S

core

PT 5/11 - PT-WFD

lab code result [µg/l] ± ζ-score z-score assessm.1 0,414 -0,4 s2 0,504 0,034 2,5 0,4 s4 0,471 0,07 0,3 0,1 s6 0,497 0,3 s8 0,449 -0,1 s9 0,394 -0,6 s

15 0,444 -0,2 s17 0,505 0,03 2,8 0,4 s18 0,547 0,7 s20 0,325 0,137 -2,0 -1,2 s22 0,4926 0,148 0,4 0,3 s23 0,2651 -1,7 s24 0,4695 0,1 s27 0,079 0,04 -19,1 -3,3 u28 0,3725 -0,8 s29 0,48 0,2 s30 0,529 0,6 s31 0,449 0,09 -0,3 -0,1 s32 0,398 0,001 -40,1 -0,6 s35 0,427 0,044 -1,6 -0,3 s37 0,8723 3,6 u38 0,396 -0,6 s39 0,4336 -0,2 s41 0,421 -0,4 s

page C-115 of C-117



cybutryne - 30,46210,69320,2311

± 0,003PT 5/11 - WFD

PT 5/11 - PT-WFD

page C-116 of C-117

cybutryne - 3

0

0,1

0,2

0,3

0,4

0,5

0,6

0,7

0,8

0,9

127 23 20 28 9 38 32 1 41 35 39 15 8 31 24 4 29 22 6 2 17 30 18 37

lab code

con

cen

trat

ion

in µ

g/l

cybutryne - 3

-4

-3

-2

-1

0

1

2

3

4

27 23 20 28 9 38 32 1 41 35 39 15 8 31 24 4 29 22 6 2 17 30 18 37

lab code

z-sc

ore

PT 5/11 - PT-WFD

page C-117 of C-117

cybutryne - 3

0

0,02

0,04

0,06

0,08

0,1

0,12

0,14

0,1632 17 2 27 35 4 31 20 22

lab code

exp

and

ed u

nce

rtai

nty

cybutryne - 3

-45

-40

-35

-30

-25

-20

-15

-10

-5

0

5

32 27 20 35 31 4 22 2 17

lab code

ζ-S

core

analytische qualitätssicherung baden-württemberg · relative standard deviation and tolerance...

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