Priority. Profic. iency. University of Stuttgart

Transcription

1 Analytische Qualitätssicherung Baen-Württemberg PT-WFD Profic iency Priority pesticies Test 6/ in surface water aclonifen, alachlor, atrazine, bifenox, chlorfenvinphos, chlorpyrifos, cybutryne, iuron, isoproturon, quinoxyfen, simazine, terbutryn, trifluralin provie by AQS Baen-Württemberg at Institute for Sanitary Engineerin g, Water Quality an Soli Waste Management, University of Stuttgart Bantäle 2, 7056 Stuttgart-Büsnau, Germanyy in cooperation with other European PT P proviers Stuttgart, in January 4

2 Responsibilities: Scientific irector AQS: Dr.-Ing. Dipl.-Chem. Michael Koch PT manager: Dr.-Ing. Frank Baumeister AQS Baen-Württemberg at Institute of Sanitary Engineering, Water Quality an Soli Waste Management at University of Stuttgart Bantäle Stuttgart-Büsnau Germany Tel.: +4 (0)7 / Fax: +4 (0)7 / info@aqsbw.e

3 PT-WFD priority pesticies INDEX OF CONTENTS. GENERAL PT DESIGN SAMPLE PREPARATION SAMPLE DISTRIBUTION ANALYTICAL METHODS SUBMISSION OF RESULTS EVALUATION AND ASSESSMENT.... PARTICIPATION.... EXPLANATION OF APPENDIX A EXPLANATION OF APPENDIX B EXPLANATION OF APPENDIX C MEASUREMENT UNCERTAINTY TRACEABLE REFERENCE VALUES INTERNET... Appenix A ACLONIFEN... A- ALACHLOR... A- ATRAZINE... A-6 BIFENOX... A-2 CHLORFENVINPHOS... A-0 CHLORPYRIFOSETHYL... A- CYBUTRYNE... A-46 DIURON... A-5 ISOPROTURON... A-6 QUINOXYFEN... A-6 SIMAZINE... A-75 TERBUTRYN... A-2 TRIFLURALIN... A- Appenix B

4 PT-WFD priority pesticies Appenix C ACLONIFEN... C- ALACHLOR... C-0 ATRAZINE... C- BIFENOX... C-2 CHLORFENVINPHOS... C-7 CHLORPYRIFOSETHYL... C-46 CYBUTRYNE... C-55 DIURON... C-64 ISOPROTURON... C-7 QUINOXYFEN... C-2 SIMAZINE... C- TERBUTRYN... C-00 TRIFLURALIN... C-0

5 PT-WFD priority pesticies page. General This PT was provie by AQS Baen-Württemberg in the context of the PT-WFD network of European PT proviers for the etermination of: aclonifen alachlor atrazine bifenox chlorfenvinphos chlorpyrifos (chlorpyrifos-ethyl) cybutryne iuron isoproturon quinoxyfen simazine terbutryn trifluralin The PT met the requirements of the water framework irective an the relate environmental quality stanars for the etermination of priority substances in surface water. The PT was organize in collaboration with the following other PT proviers in Europe: QualityConsult, Via G. Bettolo 4, (005) Rome Italy, Tel.: , Fax: , qualityconsult@aqc.it Proftest SYKE Finnish Environment Institute, Laboratories, Hakuninmaantie 6, FI Helsinki, FINLAND, Tel: , Fax: +5 44, proftest@environment.fi The PT was execute an evaluate accoring to the requirements of the PT-WFD network.

6 PT-WFD priority pesticies page 2 2. PT esign Each participant receive the following samples: - samples for the etermination of the above mentione parameters in two 000 ml-glass bottles each, screw cappe with PTFE sealing. The samples were preserve by cooling. ifferent concentration levels/batches were prouce.. Sample preparation The samples were base on a real surface water. The surface water was sieve to eliminate course particles, but not filtere. To reuce germs, the surface water was irraiate with ultraviolet light. For preparation of the samples, the surface water was spike with a solution of the substances issolve in DMF. The concentrations of the analytes in the spike samples was base on the analytical feasibility an on the values of article 4 of the commission irective 0/0/EC of the European communities for the technical specifications for chemical analysis an monitoring of water status in the context of the water framework irective. Accoring to Directive 0/05/EG on environmental quality stanars in the fiel of water policy, the AA-Environmental Quality Stanar values are as follows: Parameter (propose) AA-EQS [µg/l] aclonifen (0,) alachlor 0, atrazine 0,6 bifenox (0,025) chlorfenvinphos 0, chlorpyrifos (chlorpyrifos-ethyl) 0,0 cybutryne (0,006) iuron (0,) isoproturon quinoxyfen (0,065) simazine 0,0 terbutryn (0,) trifluralin 0, AA: annual average The samples were coole irectly after preparation an ispatche with freezer packs ae to the packages. 4. Sample istribution The samples were ispatche on 07 th October by express service. Laboratories registere at one of the cooperating PT proviers receive the samples from there. The participants were informe to store the samples uner coole conitions irectly after receipt an to start with the analysis of the samples as soon as possible, but one ay after receipt at the latest.

7 PT-WFD priority pesticies page 5. Analytical methos The participants were free to choose a suitable metho, but a maximum limit of quantification (LOQ) for all parameters of 0,025 µg/l was require. Accoring to Commission Directive 0/0/EC, Technical specifications for chemical analysis an monitoring of water status, the limit shoul correspon to 0% of the environmental stanars of the irective 0/05/EG on environmental quality stanars in the fiel of water policy. Since the irective requirements in this case are not always achievable, the LOQ was chosen accoring to common practice (see also chapter sample preparation ). The samples ha to be analyse in uplicate over the complete metho (sample preparation an measurement). The participants were aske to submit the results as average values in µg/l with four significant igits. 6. Submission of results The ealine for the submission of results was on 2 th October. 7. Evaluation an assessment Accoring to the agreements in the PT-WFD network the following proceure was use for the evaluation an assessment of the PT roun: The reference values (see chapter Traceable reference values ) were use as assigne value X. A fixe value of 25% of the assigne value was use as stanar eviation for proficiency assessmentσ ). For each measurement result of the participant a z-score was calculate using the following formula: z = x ) X σ For the assessment the following criteria were use: z 2,0 satisfactory 2,0 < z <,0 questionable z,0 unsatisfactory. Participation Number of participants (total): 2 Registration via: AQS Baen-Württemberg, Germany: 25 QualityConsult, Italien: 2 SYKE, Finlan: 2 Figure shows the number of percentage of satisfactory, questionable, unsatisfactory results an not submitte results.

8 PT-WFD priority pesticies page 4 Figure : results. Percentage of satisfactory, questionable, unsatisfactory an not submitte. Explanationn of Appenix A Appenix A contains for each parameterr parameter tables a figure of participants means (calculate with Algorithm A) versus the spike amounts for the etermination of the recovery rate an the matrix content a figure of the relative stanar eviations versus the concentrations a figure of the tolerancee limits in the PT versus the concentrations the frequency of application of analytical methos the metho specific evaluation a comparison of mean an reference values for each concentration level a comparison of the relative stanar eviations of thee ifferent methos the statistical characteristics of the metho specific evaluation a tabular comparison off the means with the reference values an their uncer- tainties Parameter tables In these tables the following values for each concentration level are liste: assigne value expane uncertainty of the assigne value in % (seee chapter Traceable ref- erence values ) stanar eviation, calculate using robust statistical metho (Algorithm A) stanar eviation for proficiency y assessment in µg/l for f the calculation of z- scores (25 % of the assigne value) rel. stanar eviation for f proficiency assessment in % tolerance limits above an below in µg/l an % number of values in this level number of not satisfactory values below an above the assigne value an the percentage of these values in total.

9 PT-WFD priority pesticies page 5 Determination of recovery rate In the iagrams of the mean valuess versus the spike amount a of analyte a linear re- takes gression line was calculate using a generalize least square s regression which into account the uncertainties of thee values in both irections. From this regression line the recovery rate for each parameter was etermine (see iagrams). The slope of the line inicates the average recovery rate an the x-axis x intercept correspons to the matrix content. Since in the present case the surface water use was not exmatrix con- pecte to contain the pesticies to be analyse an thee uncertainty of the tent calculation from the iagrams were always higher than t the value itself, it was ecie not to use any matrix content for the calculationn of reference values for this PT roun. The iagrams also contain the expane uncertainty (k=2) of the spike amount an the mean values. Figure 2 gives an overview of all average recovery rates for all parameters. Figure 2: Average recovery rates for all parameters Relative stanar eviation an tolerancee limit The iagrams for the rel. stanar eviation vs. the assigne value show the values compare to the fixe stanar eviation for proficiencyy assessment (horizontal line at 25%) an the concentration epenence. The iagrams with the tolerance limits show the limits in percent. Metho specific evaluation For each parameter the methos use by the participants are shown in a iagram. In a secon iagram for each metho values are sorte in 5 categories: too low low correct high too high results with z-score < -2 results with 2 z-score < results with z-score + results with + < z-score +2 results with z-score > +2 Comparison of means an reference values for each concentration level Finally the mean value calculate from all results (Algorithm A) an the reference value are compare with mean values calculate for all methos separately (in this

10 PT-WFD priority pesticies page 6 case using the Hampel estimator escribe in ISO/TS 62). Mean values were calculate only, if more than 7 results were within a z-score-range of ± 2. The means are reporte with their expane uncertainty calculate accoring to ISO Explanation of Appenix B Participants were aske to report expane uncertainties of their results on a voluntary basis. In this iagram for each parameter the reporte uncertainties for all concentration levels with the reproucibility stanar eviation (horizontal line) are isplaye. Values which eviate from the reproucibility stanar eviation with a factor more than 2 are usually not realistic.. Explanation of Appenix C In the last part of the report, for all concentration levels the results of all participants are illustrate. Confientiality of participants is ensure by using lab coes. The lab coes were sent to participants with the certificates. In etail Appenix C contains: a table with all ata figures with o all reporte results o all z-scores o all reporte expane uncertainties o all ζ scores Table with all ata The assigne value with the expane uncertainty an the tolerance limits for the concentration level is illustrate in the table. For each participant the following ata are given: lab coe reporte result measurement uncertainty of the value (if reporte) ζ-score for this value, calculate with the following formula ζ = x x 2 2 u lab + u ref, with x x = ifference from the measure value an the assigne value u lab = stanar uncertainty of the value, reporte by the participant u ref = stanar uncertainty of the assigne value z-score for proficiency assessment assessment of the value accoring 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 ata are normally istribute an the uncertainties are well estimate, ζ-scores will lie between -2 an +2 with a probability of aroun 5 %. ζ-scores are mainly influence by the measurement uncertainties reporte by the laboratory. Therefore ζ-scores are usually not appropriate for the assessment of the reporte results, unless the reporte measurement uncertainty is checke for fitnessfor-purpose.

11 PT-WFD priority pesticies page 7 Therefore we o not use the ζ-scores for the assessment of the laboratories. Nevertheless ζ-scores are appropriate to check the plausibility of the reporte measurement uncertainty: If the z-score of a result is within the tolerance limit an the ζ-score is outsie, then the measurement uncertainty is unerestimate. If the z-score is outsie the tolerance limits an the absolute value of the ζ-score is lower than two, then the requirements of the proficiency test were stronger compare with the reporte measurement uncertainty. Diagrams of uncertainty ata: In the first figure for all lab coes the measurement uncertainty (together with the reproucibility stanar eviation) is illustrate. The secon figure shows the associate ζ-scores. 2. Measurement uncertainty 6 (57,%) out of 2 laboratories with vali values reporte measurement uncertainties. In total 504 (54,%) out of vali values were given with the measurement uncertainty. The following table isplays the number of values with measurement uncertainty against the accreitation status. Accreitation status of the values Number of values Number of values with measurement uncertainty accreite (62,6%) not accreite 2 6 (56,%) not specifie (2,6%) We woul like to put emphasis on the fact that reporting of measurement uncertainties in our PT scheme is absolutely voluntary. The only objective is to help all participants to reasonably hanle measurement uncertainties an their estimation. The iagrams show that the sprea of reporte uncertainties in some cases is vast, in many cases unrealisticly low values were reporte. A plausibility check using reproucibility stanar eviations of the PT roun coul be helpful here. If measurement uncertainties are unerestimate values, assesse as satisfactory in the PT ( z 2), will have a large ζ-score. ζ > 2 means that the own requirements (efine in terms of estimate uncertainty) are not fulfille. 25 (26,5%) out of the 47 values reporte with uncertainties an having a z-score z 2.0 ha a ζ-score > 2.0. This means that the requirements of the PT scheme have been fulfille, but not the own requirements, the uncertainty is unerestimate.. Traceable reference values Traceability of analytical results to national an international references is of increasing importance in all laboratories. This is not easy to realise for chemical analyses an often can only be one by analysing certifie reference materials. But availability of these reference materials in the water sector is very limite. Therefore we try to provie reference values for the proficiency test samples, traceable to national an international references. Since our PT samples without exception are spike, real water samples, reference values can be calculate from the sum of matrix content an spike amount of analyte. For both summans traceable values an their uncertainty have to be etermine. Thereby we assume that no unrecognise bias resulting from sample preparation an transport is present an that we recognise all uncertainty components.

12 PT-WFD priority pesticies page Determination of the spike amount an its uncertainty All spiking of samples was controlle gravimetrically. Conversion to concentration was one by measuring the ensity of the resulting samples using a pycnometer. This proceure allows the formulation of a complete uncertainty buget. The first step is the specification of the measuran with a formula. This shows the links between the result an all influence quantities: c lot = m subst_ ss P m ss m m ss _ il il m m lot il _ lot K ρ lot with: c lot m subst_ss m ss_il m il_lot m ss m il m lot ρ lot P K concentration of the analyte in the lot resulting from the spike in g/l mass of the stanar ae for preparation of the stock solution in g mass of stock solution ae for preparation of ilution in g mass of ilution ae for preparation of the lot in g total mass of stock solution in g total mass of ilution in g total mass of the lot in g ensity of the lot in g/l purity of the stanar buoyancy correction Base on this formula the uncertainty buget can be prepare an all components can be quantifie. The following figure shows a typical istribution of the contributions, here for atrazine as an example. The main contribution results from the uncertainty of the concentration of the stanar. The purity of the stanar (%) an the uncertainty of the concentration (expane uncertainty: 0,5%) was taken from the certificate of the supplier. 0 5E- E-0,5E-0 2E-0 2,5E-0 weighing substance in g purity weighing in ilution in g weighing in lot in g ensity in g/l total mass of stock solution in g total mass of ilution in g total mas lot in g buoyancy correction All weighings were one as ifference weighings. The uncertainty of these weighings were taken from the calibration certificate of the balance prepare by an accreite calibration laboratory.

13 PT-WFD priority pesticies page The etermination of the ensity was also mae using weighings (of the pycnometer). The above sai also applies here. Temperature measurement was mae with a calibrate thermometer. The purity of the use atrazine was taken from the certificate of the manufacturer. With all these uncertainty components the combine uncertainty, as escribe in the EURACHEM/CITAC-Guie Quantifying Uncertainty in Analytical Measurement, was calculate using the sensitivity coefficients etermine by partial erivation of the formula to the respective influence quantities. So traceability was assure by using calibrate balances an thermometers. Determination of the matrix content Because the same matrix was use for preparation of all samples, the matrix content coul be calculate from the mean values of the participants an the spike amounts in a stanar-aition-like way,2. The uncertainties of the spike amounts were known from the uncertainty bugets. The expane uncertainties of the mean values of participants result were calculate accoring to ISO 2 (Statistical Methos for Use in Proficiency Testing by Interlaboratory Comparisons) as u mean with: sr = 2, 25 n s R reproucibility stanar eviation n number of ata for this level 2 coverage factor for the expane uncertainty,25 correction factor (accoring to ISO 2 to be use for robust methos) The content of the matrix can be erive from a linear regression of means vs. spike amounts. Since uncertainties of all ata points were available for x- as well as y-irection a generalise least square regression was use as escribe in DIN EN 64. The computer program B_LEAST (from BAM) was use for this purpose. With this metho a value for matrix an its uncertainty are obtaine. Because of statistical variation of the input values the calculate 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 en of the uncertainty range of the matrix content also might be negative. Therefore the expane uncertainty of the matrix content was set to the matrix content itself in this case. The matrix content is not irectly traceable to national or international references, but it oes not consierably compromise the traceability of the final content ue to its comparably low contribution. As state above the matrix content in the present PT roun was negligible for all parameters. Therefore the matrix content was not consiere in the calculation of the assigne values. 4. Internet These report also is available from the following internet aress: Rienitz, O., Schiel, D., Güttler, B., Koch, M., Borchers, U.: A convenient an economic approach to achieve SI-traceable reference values to be use in rinking-water interlaboratory comparisons. Accre Qual Assur (07) 2: Koch, M., Baumeister, F.: Traceable reference values for routine rinking water proficiency testing: first experiences. Accre Qual Assur (0) : 77-2.

14 aclonifen level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,07,60 0,0244 0,024 25,00 0,46 0,04 50,00-50, ,0 2 0,022 4,2 0,042 0, ,00 0,45 0, 50,00-50, , 0,5705, 0,02 0,426 25,00 0,557 0,252 50,00-50, , sum , out [%] Recovery an matrix content e n e n Slope of the regression: 0,, recovery:,% Neg. x-axis intercept = matrix content: 0,04 µg/l Expane uncertainty of the matrix content: 0,04 µg/l = 00% page A- of A-5

15 Relative stanar eviation an tolerance limits l e n The relative stanar eviation, calculate with Algorithm A, reache the stanar eviation for proficiency assessment of 25% at one concentration level. e l e e n page A-2 of A-5

16 Metho specific evaluation e ee e e K,W>D^D^,W>D^D^ e l e HPLC-MS/MS - irect injection Others There were no significant ifferences between LC-MS an the other methos. page A- of A-5

17 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,00 0,00,7 0,07 0,06,6 2 0,2 0,0262,0 0,022 0,04 4, 0,44 0,05, 0,5705 0,02,2 K e n e page A-4 of A-5

18 K n K e e n page A-5 of A-5

19 l K Others level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 0,0 0,007,57 0,02 25, ,2 2 0,22 0,04 6,25 0,04,74 4 4,2 0,47 0,0,07 0, 24, ,2 robust stanar eviation [%] number of results out below out above out [%] page A-6 of A-5

20 page A-7 of A-5

21 alachlor level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,06 6,4 0,007 0,07 25,00 0,040 0,047 50,00-50, ,2 2 0,4 2,2 0,056 0,00 25,00 0,640 0,260 50,00-50, , 0,5672 2, 0,075 0,4 25,00 0,50 0,26 50,00-50, ,0 sum ,0 out [%] Recovery an matrix content e n e e n Slope of the regression: 0,, recovery:,% Neg. x-axis intercept = matrix content: 0,004 µg/l Expane uncertainty of the matrix content: 0,004 µg/l = 00% page A- of A-5

22 Relative stanar eviation an tolerance limits l e n The relative stanar eviation, calculate with Algorithm A, i not reach the stanar eviation for proficiency assessment of 25%. e l e e n page A- of A-5

23 Metho specific evaluation e ee,w>d^d^ K,W>D^D^ e e l e e HPLC-MS/MS - extraction Others HPLC-MS/MS - irect injection The values etermine with LC-MS/MS irect injection showe the closest istribution. page A-0 of A-5

24 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,06 0,006 5, 0,06 0,0044 6,4 2 0,44 0,026 6, 0,4 0,00 2, 0,507 0,0446, 0,5672 0,025 2,2 e e e n,w>d^d^ K page A- of A-5

25 ,W>D^D^ K n,w>d^d^ K e e n page A-2 of A-5

26 l,w>d^d^ K HPLC-MS/MS - irect injection level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 0,06 0,002,522 0,006,44 0 2, 2 0,402 0,04,575 0,0, ,54 0,0,647 0,052, robust stanar eviation [%] number of results out below out above out [%] page A- of A-5

27 Others level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 2 0,6 0,025 6, 0,06 7, ,45 0,05 7,675 0,0, robust stanar eviation [%] number of results out below out above out [%] page A-4 of A-5

28 page A- of A-5

29 atrazine level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,04 2,26 0,00 0,022 25,00 0,274 0, ,00-50,00 2 0,6 2 0,422 2,04 0,0450 0,07 25,00 0,6424 0,24 50,00-50,00 2 0,6 0,6426 2,0 0,074 0,607 25,00 0,6 0,2 50,00-50,00 2 0,6 sum 4 0,6 out [%] Recovery an matrix content e e n e e n Slope of the regression: 0,, recovery:,% Neg. x-axis intercept = matrix content: 0 µg/l Expane uncertainty of the matrix content: 0,000 µg/l = 0% page A-6 of A-5

30 Relative stanar eviation an tolerance limits l e e n The relative stanar eviation, calculate with Algorithm A, i not reach the stanar eviation for proficiency assessment of 25%. e l e e e n page A-7 of A-5

31 Metho specific evaluation ee ee e e e e,w>d^d^,w>d^d^ 'D^^WK,W>hs^W'D^>> e e e l e HPLC-UV/SPE Others GC-MS/SPE HPLC-MS/MS - extraction HPLC-MS/MS - irect injection The values, etermine with LC-MS/MS irect injection, showe the closest istribution. The ifferences between the other methoes were not significant. page A- of A-5

32 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,070 0,004 6,0 0,04 0,00 2, 2 0,402 0,022 5,2 0,422 0,007 2,0 0,525 0,070 6,4 0,6426 0,0 2,0,W>D^D^ e e e e n page A- of A-5

33 ,W>D^D^ n,w>d^d^ e e n page A- of A-5

34 e l e e,w>d^d^ HPLC-MS/MS - irect injection level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 0,07 0,004 5,054 0,0 4,0 2 0, 2 0,404 0,0,0 0,04 0, 0,0 0,56 0,0 5, 0,06 4, 2 0, robust stanar eviation [%] number of results out below out above out [%] page A-2 of A-5

35 page A-22 of A-5

36 bifenox level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,6,7 0,0 0,02 25,00 0,75 0,057 50,00-50,00 77, 2 0,4 2,07 0,05 0,24 25,00 0,746 0,245 50,00-50,00 0 6, 0,7076 2,0 0,05 0,76 25,00,06 0,5 50,00-50, ,2 sum ,4 out [%] Recovery an matrix content e n e e e n Slope of the regression: 0,66, recovery: 6,6% Neg. x-axis intercept = matrix content: 0 µg/l Expane uncertainty of the matrix content: 0,005 µg/l = 0% page A-2 of A-5

37 Relative stanar eviation an tolerance limits l e e e n The relative stanar eviation, calculate with Algorithm A, reache the stanar eviation for proficiency assessment of 25% with one concentration level. e l e e e e n page A-24 of A-5

38 Metho specific evaluation e e K,W>D^D^,W>D^D^ e e l HPLC-MS/MS - extraction HPLC-MS/MS - irect injection Others The application of all methos lea to low values. page A-25 of A-5

39 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,07 0,0,6 0,6 0,004,7 2 0, 0,047 0, 0,4 0,00 2, 0,40 0,0560 2, 0,7076 0,042 2,0 K n e e page A-26 of A-5

40 K e n K e e e n page A-27 of A-5

41 l K Others level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 0,072 0,0,7 0,025 4, ,7 0,02,2 0,072 22, ,4 0,052, 0, 2, robust stanar eviation [%] number of results out below out above out [%] page A-2 of A-5

42 page A-2 of A-5

43 chlorfenvinphos level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,77 4,7 0,026 0,024 25,00 0,766 0,05 50,00-50, ,0 2 0,272 2,2 0,0540 0,060 25,00 0,40 0,60 50,00-50, ,0 0,472 2, 0,06 0,2 25,00 0,70 0,264 50,00-50, ,0 sum , out [%] Recovery an matrix content e n e n Slope of the regression:,2, recovery: 2,% Neg. x-axis intercept = matrix content: 0 µg/l Expane uncertainty of the matrix content: 0,005 µg/l = 0% page A-0 of A-5

44 Relative stanar eviation an tolerance limits l n The relative stanar eviation, calculate with Algorithm A, i not reach the stanar eviation for proficiency assessment of 25%. e l e n page A- of A-5

45 Metho specific evaluation e e e e,w>d^d^ K,W>D^D^ e e e l e HPLC-MS/MS - extraction Others HPLC-MS/MS - irect injection The values etermine with LC-MS - irect injection showe the closest istribution. page A-2 of A-5

46 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,25 0,02 0,7 0,77 0,0056 4, 2 0, 0,0270,5 0,272 0,0077 2, 0,5025 0,040,6 0,472 0,00 2, e n e e,w>d^d^ K page A- of A-5

47 ,W>D^D^ K n,w>d^d^ K e n page A-4 of A-5

48 l,w>d^d^ K HPLC-MS/MS - irect injection level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 0, 0,007 6,22 0,02 7,52 2 0, 2 0,02 0,022 7,26 0,06, ,45 0,02 6,47 0,0 7, robust stanar eviation [%] number of results out below out above out [%] page A-5 of A-5

49 Others level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] robust stanar eviation [%] number of results out below out above out [%] 0,22 0,0,75 0,026 2,02 0, page A-6 of A-5

50 page A-7 of A-5

51 chlorpyrifos-ethyl level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,6 0,7 0,027 0,027 25,00 0,674 0,055 50,00-50, , 2 0,442 2,57 0,0 0,25 25,00 0,74 0,247 50,00-50, ,2 0,77, 0,6 0,5 25,00,76 0, 50,00-50, ,7 sum ,7 out [%] Recovery an matrix content e e e n e e e e n Slope of the regression: 0,6, recovery:,6% Neg. x-axis intercept = matrix content: 0,02 µg/l Expane uncertainty of the matrix content: 0,02 µg/l = 00% page A- of A-5

52 Relative stanar eviation an tolerance limits l e e e e n The relative stanar eviation, calculate with Algorithm A, reache the stanar eviation for proficiency assessment of 25% with all concentration levels. e l e e e e e n page A- of A-5

53 Metho specific evaluation e e e e K,W>D^D^,W>D^D^ e e l HPLC-MS/MS - irect injection Others There were no significant ifferences between LC-MS an the other methos. page A-40 of A-5

54 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,00 0,0, 0,6 0,04 0,2 2 0,40 0,055, 0,442 0,027 2,6 0,676 0,065 6,7 0,77 0,047, K,W>D^D^ n e e page A-4 of A-5

55 K,W>D^D^ e n K,W>D^D^ e e e e n page A-42 of A-5

56 l K,W>D^D^ Others level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 0,0 0,00, 0,024 27,2, 2 0,40 0,0, 0,02 25,4 0 6,667 0,67 0,05,4 0, 2,2 2 0, robust stanar eviation [%] number of results out below out above out [%] page A-4 of A-5

57 HPLC-MS/MS - irect injection level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] robust stanar eviation [%] number of results out below out above out [%] 2 0,446 0,06,7 0, 0, page A-44 of A-5

58 page A-45 of A-5

59 cybutryne level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,06 5,52 0,072 0, ,00 0, 0,050 50,00-50, ,6 2 0,257 2,67 0,02 0,064 25,00 0,5 0,2 50,00-50, ,6 0,52, 0,064 0,0 25,00 0,7 0, ,00-50, , sum ,0 out [%] Recovery an matrix content e n e n Slope of the regression: 0,4, recovery: 4,% Neg. x-axis intercept = matrix content: 0,0055 µg/l Expane uncertainty of the matrix content: 0,0055 µg/l = 00% page A-46 of A-5

60 Relative stanar eviation an tolerance limits l e n The relative stanar eviation, calculate with Algorithm A, i not reach the stanar eviation for proficiency assessment of 25%. e l e e n page A-47 of A-5

61 Metho specific evaluation ee ee e,w>d^d^ K,W>D^D^ e e l e e HPLC-MS/MS - extraction Others HPLC-MS/MS - irect injection The values etermine with LC-MS - irect injection showe the closest istribution. page A-4 of A-5

62 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,0 0,004,4 0,06 0,005 5,5 2 0,250 0,060 6,4 0,257 0,006 2,7 0,45 0,054 7,2 0,52 0,000,,W>D^D^ e n e page A-4 of A-5

63 ,W>D^D^ n,w>d^d^ e n page A-50 of A-5

64 e e l e e,w>d^d^ HPLC-MS/MS - irect injection level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 0,04 0,006 5,67 0,0 4, ,26 0,00,5 0,024, ,52 0,027 5,065 0,067 2, robust stanar eviation [%] number of results out below out above out [%] page A-5 of A-5

65 page A-52 of A-5

66 iuron level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,00,42 0,02 0, ,00 0,2 0, ,00-50, ,0 2 0,40 2,5 0,07 0,2 25,00 0,7 0, ,00-50, ,0 0,674,2 0,0765 0,7 25,00,0 0,47 50,00-50, ,0 sum 75 4,0 out [%] Recovery an matrix content e e e n e e e n Slope of the regression: 0,27, recovery: 2,7% Neg. x-axis intercept = matrix content: 0,004 µg/l Expane uncertainty of the matrix content: 0,004 µg/l = 00% page A-5 of A-5

67 Relative stanar eviation an tolerance limits l e e e n The relative stanar eviation, calculate with Algorithm A, i not reach the stanar eviation for proficiency assessment of 25%. e l e e e e n page A-54 of A-5

68 Metho specific evaluation e e e,w>d^d^,w>d^d^ K,W>hs^W e e l e e HPLC-UV/SPE Others HPLC-MS/MS - extraction HPLC-MS/MS - irect injection The values etermine with HPLC-UV/SPE an LC-MS - irect injection showe the closest istribution. page A-55 of A-5

69 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,05 0,0076, 0,00 0,005,4 2 0,440 0,00,7 0,40 0,0 2,4 0,6 0,0 6,0 0,674 0,02,,W>D^D^,W>D^D^ e n e page A-56 of A-5

70 ,W>D^D^,W>D^D^ e n,w>d^d^,w>d^d^ e e e n page A-57 of A-5

71 l,w>d^d^,w>d^d^ HPLC-MS/MS - irect injection level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 0,05 0,002 2,07 0,005 5,75 2 6,67 2 0,46 0,02 4,57 0,05 2, ,66 0,02,524 0,065, , robust stanar eviation [%] number of results out below out above out [%] page A-5 of A-5

72 HPLC-MS/MS - extraction level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 2 0,46 0,07 6,2 0,6 6, ,606 0,075 2,44 0,7 2, robust stanar eviation [%] number of results out below out above out [%] page A-5 of A-5

73 page A-60 of A-5

74 isoproturon level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,052,02 0,00 0,02 25,00 0,42 0, ,00-50, ,0 2 0,54 2, 0,0 0,0 25,00 0,5 0,77 50,00-50, ,0 0,600 2,26 0,050 0,0 25,00 0,045 0,0 50,00-50, ,0 sum ,7 out [%] Recovery an matrix content e e n e e n Slope of the regression: 0,, recovery:,% Neg. x-axis intercept = matrix content: 0,0 µg/l Expane uncertainty of the matrix content: 0,004 µg/l = 44,4% page A-6 of A-5

75 Relative stanar eviation an tolerance limits l e e n The relative stanar eviation, calculate with Algorithm A, i not reach the stanar eviation for proficiency assessment of 25%. e l e e e n page A-62 of A-5

76 Metho specific evaluation e e e,w>d^d^,w>d^d^ K,W>hs^W e e l e e HPLC-UV/SPE Others HPLC-MS/MS - extraction HPLC-MS/MS - irect injection The ifferences betweent the methos were not significant. page A-6 of A-5

77 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,072 0,0050 5, 0,052 0,006,0 2 0,2 0,067 5,2 0,54 0,005 2, 0,55 0,0255 4,6 0,600 0,06 2,,W>D^D^ e n e page A-64 of A-5

78 ,W>D^D^ n,w>d^d^ e e n page A-65 of A-5

79 l e e,w>d^d^ HPLC-MS/MS - irect injection level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 0,05 0,00,4 0,00 0,76 2 0, 2 0,26 0,04 4,77 0,0,5 2 0, 0,564 0,025 4, 0,06 2, robust stanar eviation [%] number of results out below out above out [%] page A-66 of A-5

80 page A-67 of A-5

81 quinoxyfen level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,076, 0,0 0,07 25,00 0,074 0,05 50,00-50, ,2 2 0,42,25 0,076 0,05 25,00 0,54 0,76 50,00-50, ,6 0,54 2,66 0,0754 0,60 25,00 0, 0,27 50,00-50,00 6,2 sum 57 5,6 out [%] Recovery an matrix content e n e n Slope of the regression: 0,7, recovery:,7% Neg. x-axis intercept = matrix content: 0,00 µg/l Expane uncertainty of the matrix content: 0,00 µg/l = 00% page A-6 of A-5

82 Relative stanar eviation an tolerance limits l e n The relative stanar eviation, calculate with Algorithm A, reache the stanar eviation for proficiency assessment of 25% with one concentration level. e l e e n page A-6 of A-5

83 Metho specific evaluation ee ee ee,w>d^d^ K,W>D^D^ e e e l e HPLC-MS/MS - extraction Others HPLC-MS/MS - irect injection The values etermine with LC-MS an extraction showe the broaest statistical istribution. page A-70 of A-5

84 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,0670 0,00 6, 0,076 0,005, 2 0,252 0,044,6 0,42 0,02, 0,5076 0,042,5 0,54 0,045 2,7,W>D^D^ e e e e n page A-7 of A-5

85 ,W>D^D^ n,w>d^d^ e e n page A-72 of A-5

86 l,w>d^d^ HPLC-MS/MS - irect injection level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] robust stanar eviation [%] number of results out below out above out [%] 0,555 0,06,02 0,47 26,44 0, page A-7 of A-5

87 page A-74 of A-5

88 simazine level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,07,0 0,00 0,02 25,00 0, 0, ,00-50, ,7 2 0,502 2,42 0,070 0,275 25,00 0,7652 0,255 50,00-50, ,7 0,75 2,0 0,0 0, 25,00,0 0,765 50,00-50, , sum 4 7,5 out [%] Recovery an matrix content e e e n e e e n Slope of the regression: 0,00, recovery: 0% Neg. x-axis intercept = matrix content: 0,004 µg/l Expane uncertainty of the matrix content: 0,004 µg/l = 00% page A-75 of A-5

89 Relative stanar eviation an tolerance limits l e e e n The relative stanar eviation, calculate with Algorithm A, i not reach the stanar eviation for proficiency assessment of 25%. e l e e e e n page A-76 of A-5

90 Metho specific evaluation ee e e e e,w>d^d^,w>d^d^ 'D^^WK,W>hs^W'D^>> e e e l e HPLC-UV/SPE Others GC-MS/SPE HPLC-MS/MS - extraction HPLC-MS/MS - irect injection The ifferences between the methos were not significant. page A-77 of A-5

91 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,072 0,006 7, 0,07 0,006, 2 0,450 0,04 7, 0,502 0,02 2,4 0,672 0,06 5, 0,75 0,07 2,,W>D^D^ e n e page A-7 of A-5

92 ,W>D^D^ e n,w>d^d^ e e e e n page A-7 of A-5

93 e e l e e,w>d^d^ HPLC-MS/MS - irect injection level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 0,076 0,00 4,27 0,00,74 2 6,67 2 0,465 0,0 4, 0,05, ,675 0,025,6 0,06 0,22 2 0, robust stanar eviation [%] number of results out below out above out [%] page A-0 of A-5

94 page A- of A-5

95 terbutryn level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,075 4,6 0,04 0,0 25,00 0,2 0,076 50,00-50, ,5 2 0,275 4,22 0,0525 0,06 25,00 0,42 0,76 50,00-50, , 0,54 2,47 0,06 0,5 25,00 0,2 0,270 50,00-50, , sum 7 5 4, out [%] Recovery an matrix content e n e n Slope of the regression: 0,72, recovery: 7,2% Neg. x-axis intercept = matrix content: 0,06 µg/l Expane uncertainty of the matrix content: 0,00 µg/l = 6,% page A-2 of A-5

96 Relative stanar eviation an tolerance limits l e n The relative stanar eviation, calculate with Algorithm A, i not reach the stanar eviation for proficiency assessment of 25%. e l e e n page A- of A-5

97 Metho specific evaluation,w>d^d^,w>d^d^ ee e K 'D^^W 'D^>> 'WE>> e e l e e GC-MS/SPE Others HPLC-MS/MS - extraction HPLC-MS/MS - irect injection The values etermine with LC-MS - irect injection showe the closest istribution. page A-4 of A-5

98 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,070 0,0072, 0,075 0,00 4,6 2 0,27 0,0252, 0,275 0,06 4,2 0,526 0,044,4 0,54 0,04 2,5,W>D^D^ e e e e n page A-5 of A-5

99 ,W>D^D^ n,w>d^d^ e n page A-6 of A-5

100 l,w>d^d^ HPLC-MS/MS - irect injection level robust mean [µg/l] exp. unc. of the mean [µg/l] exp. unc. of the mean [%] robust stanar eviation [µg/l] 0,072 0,00 4,24 0,00,75 2 0, 2 0,267 0,02 4, 0,02 2, ,67 0,524 0,024 4,52 0,067 2, robust stanar eviation [%] number of results out below out above out [%] page A-7 of A-5

101 page A- of A-5

102 trifluralin level assigne value [µg/l] expane uncertainty of the assigne value [%] stanar eviation, calculate using robust statistics [µg/l] stanar eviation for proficiency assessment [µg/l] stanar eviation for proficiency assessment [%] upper tolerance limit [µg/l] lower tolerance limit [µg/l] upper tolerance limit [%] lower tolerance limit [%] number of results out below out above 0,02 0,0 0,06 0, ,00 0,622 0,054 50,00-50, ,0 2 0,40,4 0,022 0,060 25,00 0,5760 0, 50,00-50,00 50,0 0,65 2,47 0,7 0,62 25,00 0,767 0,256 50,00-50, ,0 sum ,0 out [%] Recovery an matrix content e e n e e n Slope of the regression: 0,6, recovery:,6% Neg. x-axis intercept = matrix content: 0,007 µg/l Expane uncertainty of the matrix content: 0,007 µg/l = 00% page A- of A-5

103 Relative stanar eviation an tolerance limits l e e n The relative stanar eviation, calculate with Algorithm A, reache the stanar eviation for proficiency assessment of 25% with one concentration level. e l e e e n page A-0 of A-5

104 Metho specific evaluation 'D^>> 'D^^W K e e e l Others GC-MS/SPE GC-MS/LLE The ifferences between the methos were not significant. page A- of A-5

105 Comparison of means an reference values level mean [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] reference value [µg/l] exp. uncertainty [µg/l] exp. uncertainty [%] 0,066 0,00,4 0,02 0,00 0, 2 0,55 0,045 2, 0,40 0,02, 0,564 0,04, 0,65 0,06 2,5 n e e page A-2 of A-5

106 n e e e n page A- of A-5

107 l page A-4 of A-5

108 page A-5 of A-5

109 el l l l l l l l el el el el l l l l l l page B- of B-7

110 el el el l l l l l l el l l l l l l page B-2 of B-7

111 el l l l l l l el el el el l l l l l l page B- of B-7

112 el l l l l l l el l l l l l l page B-4 of B-7

113 el el l l l l l l l el el el el l l l l l l page B-5 of B-7

114 el el l l l l l l el l l l l l l page B-6 of B-7

115 el el el l l l l l l page B-7 of B-7

116 PT 6/ - WFD assigne value [µg/l]* upper tolerance limit [µg/l] aclonifen - 0,074 0,46 ± 0,07 lower tolerance limit [µg/l] 0,047 lab coe result [µg/l] ± ζ-score z-score assessm. 0,04 0,02-6,6-2,4-0,0 0,02 -,6-0, + 6 0,077-0, + 7 0,0 0,0 -,2-0,5 + 0,25 0,0,,0 + 0,066 0,0 -, -,4 + 0,0-0,4 + 0,066 0,07-2, -, ,05 0,02-0, -0,2 + 0,0-0, + 0, 0,0 2,2,6-0,074 0,0-2,5 -, ,0464-0, ,07 -, + 2 0,4 0,6 + 0,0606 0,027-2,6 -, ,05-0, ,0565-0, ,074 0,0-2,5 -, ,07-0, + 0,06-2,6-0, 0,05,, - * The state uncertainty of the assigne value is the expane uncertainty with a coverage factor k=2 corresponing to a confience level of about 5% page C- of C-7

117 n page C-2 of C-7

118 e e e e n e e e ζ ^ page C- of C-7

119 PT 6/ - WFD assigne value [µg/l]* upper tolerance limit [µg/l] aclonifen - 2 0,022 0,45 ± 0,04 lower tolerance limit [µg/l] 0, lab coe result [µg/l] ± ζ-score z-score assessm. 0,57 0,2,4, + 0, 0,04-5, -, ,242-0, + 7 0,45 0,02-7,5 -,6 + 0,22 0,066-2,4 -, + 0,22 0,06 -,7 -,2 + 0,26-0,4 + 0,2276 0,057-2,5 -, ,2 0,05-0,4-0, + 0,25-0,6 + 0,6 0,0,4 0, + 0,2 0,04 -, -, + 2 0,276-0, ,225 -, ,252-0,2 + 0,202 0,05 -, -, ,2245 -, ,274-0, , 0,06-6, -, ,2-0, + 0,027-2, - 0,56 0,05 0,2,5 - * The state uncertainty of the assigne value is the expane uncertainty with a coverage factor k=2 corresponing to a confience level of about 5% page C-4 of C-7

120 e n page C-5 of C-7

121 e e n e e e e ζ ^ page C-6 of C-7

122 PT 6/ - WFD assigne value [µg/l]* upper tolerance limit [µg/l] aclonifen - 0,5705 0,557 ± 0,02 lower tolerance limit [µg/l] 0,252 lab coe result [µg/l] ± ζ-score z-score assessm. 0,62 0,06-22,5 -,2-0,46 0,2-2,2-0, + 6 0,55-0, + 7 0,565 0,054-7,6 -,5 + 0,40 0,22-2,6 -, + 0,552 0,276-0, -0, + 0,5 0, + 0,454 0,4-2,0-0, + 7 0,5 0,7 0, 0,2 + 0,55-0,2 + 0,6 0,0 2, 0, + 0,5 0,0-4,5 -, + 2 0,56-0, ,52-0, + 2 0,404 -, + 0,52 0,2-0,5-0, ,445-0, ,607 0, + 6 0,45 0,0-2,7-0, + 7 0,54-0,2 + 0,2-2,7-0,54 0,05-0, -0,2 + * The state uncertainty of the assigne value is the expane uncertainty with a coverage factor k=2 corresponing to a confience level of about 5% page C-7 of C-7

123 e e e e n page C- of C-7

124 n ^ ζ page C- of C-7

125 PT 6/ - WFD assigne value [µg/l]* upper tolerance limit [µg/l] alachlor - 0,06 0,04 ± 0,00445 lower tolerance limit [µg/l] 0,0465 lab coe result [µg/l] ± ζ-score z-score assessm. 0,402 0,72 4,0,6-2 0,0605 0,024-0,7-0,5 + 0,055 0,02 -,4-0, + 5 0,057 0,00-2,4-0, ,0545-0, + 0,062 0,0-0,7-0,4 + 0,0564 0,02-0, -0, ,0554 0,005-4, -0, + 0,0 0,6 + 0,05 0,0 -, -0, ,05 0,07 -, -0,7 + 0,06-0,5 + 0,06 0,05-0,4-0,5 + 0,05 0,0 -, -0, ,0724 0, ,066-0, ,257 0,5-0,0672 0,0-0, -0, + 2 0, , ,064-0, + 6 0,05 0,0 -, -0, ,06-0,5 + 0,064 -, + 0,0554 0,05-0,6-0, + * The state uncertainty of the assigne value is the expane uncertainty with a coverage factor k=2 corresponing to a confience level of about 5% page C-0 of C-7

126 n page C- of C-7

127 e e e e n ζ ^ page C-2 of C-7

128 PT 6/ - WFD assigne value [µg/l]* upper tolerance limit [µg/l] alachlor - 2 0,42 0,64 ± 0,00 lower tolerance limit [µg/l] 0,26 lab coe result [µg/l] ± ζ-score z-score assessm. 0, 0,4 -,7 -, + 2 0,2672 0,07 -, -,5 + 0,406 0,0-0,6-0, ,52 0,05 -,0-0, ,60-0,7 + 0,7 0, -, -0,6 + 0,572 0,7-0, -0, ,407 0,06 -, -0,2 + 0,454 0,2 + 0,40 0,0-0,6-0, + 7 0,4 0, -0, -0,4 + 0, -0,4 + 0,42 0,05-0,5-0, + 0,2 0,06-4, -, ,47-0, ,4-0, ,56-0,7 + 0,50 0,2 0,6 0, ,422-0, ,4205 0, , 0, -0, -0, ,42-0, + 0,226 -, + 0,4 0,05 -,5-0,4 + * The state uncertainty of the assigne value is the expane uncertainty with a coverage factor k=2 corresponing to a confience level of about 5% page C- of C-7

129 e e n page C-4 of C-7

130 n e ζ ^ page C- of C-7

131 PT 6/ - WFD assigne value [µg/l]* upper tolerance limit [µg/l] alachlor - 0,5672 0,50 ± 0,025 lower tolerance limit [µg/l] 0,26 lab coe result [µg/l] ± ζ-score z-score assessm. 0,047 0,0-47, -,7-2 0,2 0,2-4,4 -, + 0,5 0, -,0-0, + 5 0,46 0,06 -,0-0, ,46-0,7 + 0,6 0, 0,5 0, + 0,47 0,26-0, -0, ,5276 0,046 -,7-0, + 0,60 0,2 + 0,5 0, -0,7-0, + 7 0,5 0,6-0,6-0, + 0,5-0,2 + 0,52 0,05 -, -0, + 0,422 0,0 -,6 -, ,577-0, ,55-0, + 2 0,07 -, + 0,62 0,2 0, 0, + 2 0,546-0, + 5 0,57 0, + 6 0,4 0, -,0-0, ,55-0, + 0,06 -, + 0,522 0,05 -, -0, + * The state uncertainty of the assigne value is the expane uncertainty with a coverage factor k=2 corresponing to a confience level of about 5% page C-6 of C-7