Peter Lepom. Umweltbundesamt, Laboratory for Water Analysis, Berlin, Germany. Requirements according WFD

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Mandate 424 to CEN for the Development and Improvement of Standards in Support of WFD - Results of the Interlaboratory Comparisons - Peter Lepom Umweltbundesamt, Laboratory for Water Analysis,

1 Mandate 424 to CEN for the Development and Improvement of Standards in Support of WFD - Results of the Interlaboratory Comparisons - Peter Lepom Umweltbundesamt, Laboratory for Water Analysis, Berlin, Germany 3rd MeeBng WG Chemicals, Brussels, 16/17 October 2014 Mandate M/424 Requirements according WFD! Analysis of whole water samples! The methods should enable the analysis of samples containing up to 0.5 g/l of suspended solids! Limits of quan>ﬁca>on equal or less than 30% EQS! Measurement uncertainty equal or less than 50%! Method should be fully in- house validated! Valida>on by European intercomparison studies according to ISO 5725 CEN Mandate 424 Results of the Interlaboratory Comparisons Page 2 1

2 Mandate M/424 Substance groups to be included! Selected polycyclic aroma>c hydrocarbons - Benzo (a)pyrene, Benzo(b)fluoranthene and benzo(k)fluoranthene, Benzo(g,h,i)- perylene and indeno(1,2,3- cd)- pyrene! Tributyl >n compounds! Organochlorine pes>cide - Alachlor, cyclodiene pesbcides (aldrin, dieldrin, endrin, isodrin), DDTs, HCHs, pentachlorobenzene, endosulfan, trichorobenzenes! Pentabromodiphenyl ether (BDEs 28, 47, 99, 100, 153, 154)! C 10 - C 13 Chloroalkanes CEN Mandate 424 Results of the Interlaboratory Comparisons Page 3 Valida.on Intercomparison PAHs ParBcipants: 18 Samples:! S1: Low level samples containing SPM (2 x 1000 ml)! S2: High level samples containing SPM (2 x 1000 ml)! S3: Sample without SPM to be spiked with the supplied solu>on (2 x 1000 ml) PreparaBon of SPM containing samples: IRMM Matrix used for preparing samples: mineral water Two procedural blanks were requested Method: pren CEN Mandate 424 Results of the Interlaboratory Comparisons Page 4 2

3 Preliminary Results Sample 1 B[b]F Sample: 1 Measurand: Benzo[b]fluoranthene Mean: 33,2 ng/l Reproducibility s.d.: 10,6 ng/l Repeatability s.d.: 5,2 ng/l C ng/l TQ Laboratory PROLab Smart for ISO CEN Mandate 424 Results of the Interlaboratory Comparisons Page 5 Summary of Preliminary Results PAHs Measurand Sample 1 Sample 2 Sample 3 n Mean CV R (%) n Mean CV R (%) n Mean CV R (%) Anthracene 10 3,44 48, ,6 48, ,2 Fluoranthene 13 51,2 41, , ,6 Benzo[b]fluoranthene 11 33,2 31, , ,9 10,8 Benzo[k]fluoranthene 11 17,4 47, ,9 17, ,5 9,0 Benzo[a]pyrene 8 13,5 19, , ,4 10,2 Benzo[ghi]perylene 10 34,2 19, , ,0 14,3 Indeno[1,2,3-cd]pyrene 7 22,5 7, , ,6 11,0 CEN Mandate 424 Results of the Interlaboratory Comparisons Page 6 3

4 Valida.on Intercomparison TBT ParBcipants: 10 Samples:! S1: Low level samples containing SPM (2x 1000 ml)! S2: High level samples containing SPM (2x 1000 ml)! S3: Sample without SPM to be spiked with the supplied solu>on (2 x 1000 ml)! S4: Blank sample (2 x 1000 ml) Matrix for sample preparabon: mineral water PreparaBon of SPM containing samples: IRMM Method: FprCEN/TS CEN Mandate 424 Results of the Interlaboratory Comparisons Page 7 Preliminary Results Sample 1 TBT Sample: 1 Measurand: TBT Ref erence value: 3,80 ng/l Mean: 4,21 ng/l Reproducibility s.d.: 2,25 ng/l Repeatability s.d.: 1,05 ng/l 9,5 9 8,5 8 7,5 7 6,5 6 ng/l 5,5 5 4,5 4 3, ,5 2 1,5 Laboratory PROLab Smart for ISO CEN Mandate 424 Results of the Interlaboratory Comparisons Page 8 4

x Summary of Preliminary Results TBT Sample l n o (%) X (µg/ L) x (µg/ L) η (%) s R (µg/l) CV R (%) S r (µg/ L) CV r (%) 1 7 14 0,0 3,8 4,21 110,8 2,25 53,4 1,05 24,9 2 7 14 0,0 3,4 3,51 103,2 1,10

5 x Summary of Preliminary Results TBT Sample l n o (%) X (µg/ L) x (µg/ L) η (%) s R (µg/l) CV R (%) S r (µg/ L) CV r (%) ,0 3,8 4,21 110,8 2,25 53,4 1,05 24, ,0 3,4 3,51 103,2 1,10 31,3 0,42 12, , ,4 102,5 2,18 12,5 1,12 6, ,0-0,32-0,20 62,5 0,10 31,3 l n o X x η sr CVR sr CVr number of laboratories after outlier rejection number of individual test results after outlier rejection percentage of outliers assigned value (reference value) overall mean of results (without outliers) recovery rate reproducibility standard deviation coefficient of variation of reproducibility repeatability standard deviation coefficient of variation of repeatability CEN Mandate 424 Results of the Interlaboratory Comparisons Page 9 Valida.on Intercomparison PBDEs ParBcipants: 14 Samples:! S1: Low level samples containing SPM (2x 1000 ml)! S2: High level samples containing SPM (2x 1000 ml)! S3: Sample without SPM to be spiked with the supplied solu>on (2 x 1000 ml)! Disclosed standard solu>on PreparaBon of SPM containing samples: IRMM Matrix for sample preparabon: mineral water Two procedural blanks were requested Method: pren CEN Mandate 424 Results of the Interlaboratory Comparisons Page 10 5

6 Preliminary Results Sample 1 Σ 6 BDEs Laboratory ng/l Sample: 1 Measurand: Sum 6 BDE Ref erence value: 1,454 ng/l 4 3,9 3,8 3,7 3,6 3,5 3,4 3,3 3,2 3,1 3 2,9 2,8 2,7 2,6 2,5 2,4 2,3 2,2 2,1 2 1,9 1,8 1,7 1,6 1,5 1,4 1,3 1,2 Mean: 1,609 ng/l Reproducibility s.d.: 0,222 ng/l Repeatability s.d.: 0,173 ng/l C PROLab Smart for ISO CEN Mandate 424 Results of the Interlaboratory Comparisons Page 11 Summary of Preliminary Results PBDEs Measurand Sample 1 Sample 2 Sample 3 n Mean CV R (%) n Mean CV R (%) n Mean CV R (%) BDE-28 <LoQ 8 0,03 25,7 <LoQ BDE ,36 15,4 9 2,64 27,1 10 0,18 25,8 BDE ,85 13,5 10 6,44 29,9 10 0,21 31,5 BDE ,13 18,9 10 0,99 34,3 9 0,05 26,5 BDE ,16 29,7 9 1,09 31,0 <LoQ BDE ,09 35,5 9 0,53 31,8 <LoQ Sum 6 BDE 9 1,61 13, ,9 27,9 10 0,51 23,5 CEN Mandate 424 Results of the Interlaboratory Comparisons Page 12 6

7 Conclusion It is possible to prepare SPM containing samples with measurand concentrabons in the pg/l or low ng/l range PAHs! Method allows analysing samples with low and high SPM content! Reproducibility for SPM containing samples between 8% and 48%! Required LoQ for B[ghi] P and Indeno[123- cd]p difficult to achieve CEN Mandate 424 Results of the Interlaboratory Comparisons Page 13 Conclusion TBT! Method allows analysing samples with low and high SPM content! Low number of par>cipants! Blank values in the range of EQS! Reproducibility for SPM containing samples between 31% and 53%! Requirements of WFD as regards LoQ were not met PBDEs! Method allows analysing samples with low and high SPM content! Reproducibility for SPM containing samples between 14% and 36%! Blank problems in some laboratories! Method meets WFD requirements CEN Mandate 424 Results of the Interlaboratory Comparisons Page 14 7

(Technische Hochschule Micelhessen - University of Applied

8 Acknowledgements The project leaders and all the parbcipants Hakån Emteborg and Saioa Elordui (IRMM) Gerhild Donnevert (Technische Hochschule Micelhessen - University of Applied Sciences) CEN Mandate 424 Results of the Interlaboratory Comparisons Page 15 8

TABLE 1A. RESULTS OF CHEMICAL ANALYSIS OF SITE WATER AND ELUTRIATE Kill Van Kull Western End SITE WATER ELUTRIATE CONSTITUENTS DETECTION LIMITS CONCEN

TABLE 1A. RESULTS OF CHEMICAL ANALYSIS OF SITE WATER AND ELUTRIATE Kill Van Kull Western End SITE WATER ELUTRIATE CONSTITUENTS DETECTION LIMITS CONCENTRATION DETECTION LIMITS CONCENTRATION Metals ppb ppb