1. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 Review of the list of priority substances (Decision 2455/2001/EC) Monitoring-based ranking methodology and results

2. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 2 Presentation based on new documents and comments made for WG E 5 “Issue paper on prioritisation process: comments, possible answers and choices made for final stage ranking” (James, 2009) “Prioritisation process : monitoring-based ranking” (James et al., 2009)

3. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 Overall data set : some figures Almost 20 000 stations on 4 water body types, Around 550 000 samplings on 3 matrices, Around 14.6 million analysis on 1151 substances 3 Among all analysis in 3 matrices, repartition is very heterogeneous: 93,2% of analysis in water 6,3% of analysis in sediments 0,5% of analysis in biota

4. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 Selection of candidate substances for the monitoring-based prioritisation exercise 4 Cut-off criterion: data submitted by more than 3 countries 316 candidate substances

5. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 5 Quality of the monitoring data : identification and treatment of non quantified values and outliers Non quantified measurements with associated DL values > 99 th percentile of DL values are discarded Threshold value = 99 th percentile of all DL values for a given substance and a given analytical fraction (provided that min(DL)  max(DL)) Distribution of DL values for a given substance and a given analytical fraction

6. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 6 Arithmetic mean 1 90th percentiles for - different substances - different analytical fractions station 2 station 1 Raw data = measures for: - different substances - different analytical fraction - different stations - different times station 3 Arithmetic mean 3 Arithmetic mean 2 Arithmetic means for - different substances - different analytical fractions - different stations PECwater PECsed, 2mm PECsed, 20µm PECsed, 63µm PECbiota, fish PECbiota, invertebrates Calculation of PEC values

7. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 7 Calculation of PEC values 2 types of PEC are calculated : PEC1 = 90th percentile of the mean per station of values >DL PEC2 = 90th percentile of the mean per station of all values, including non quantified values which are replaced by DL/2 Results in : Water Sediment Biota PEC Whole water PEC Dissolved in water (only for metals) PEC Sed 2mm PEC Sed 20µm PEC Sed 63µm PEC Fish PEC Invertebrates

8. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 8 PNEC derivation and quality objectives Ecotoxicity to aquatic organisms Secondary poisoning of predators Standards for drinking water (Dir. 98/83/EC + WHO recommendations) Ecotoxicity to benthic organisms (sediment) ADI/TDI in fish and seafood intended for human consumption Taking into account existing legislation and standards (Art. 4.9 of the WFD)

9. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 9 Risk ratios PEC2 for water, as whole water PNECwater PEC2 for water, as dissolved in water PNECwater PNECsed PEC2 for sediment, fraction 2mm PNECsed PEC2 for sediment, fraction 20 µm PNECsed PEC2 for sediment, fraction 63 µm PEC2 for biota, fish PNECoral PEC2 for biota, mollusc PNECoral PEC2 for biota, mollusc Human health ADl PEC2 for biota, fish Human health ADl Risk ratio for each substance and each analytical fraction, based on PEC2

10. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 10 Risk ratios PEC1 for water, as whole water PNECwater PEC1 for water, as dissolved in water PNECwater PNECsed PEC1 for sediment, fraction 2mm PNECsed PEC1 for sediment, fraction 20 µm PNECsed PEC1 for sediment, fraction 63 µm PEC1 for biota, fish PNECoral PEC1 for biota, mollusc PNECoral PEC1 for biota, mollusc Human health ADl PEC1 for biota, fish Human health ADl Risk ratio for each substance and each analytical fraction, based on PEC1

11. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 See Annex XI of the report 11 Priority matrix i, fraction j Definition Very high PEC2 matrix i ; fraction j / PNEC matrix i >100 AND PEC1 matrix i ; fraction j / PNEC matrix i >1 AND [ (nb anal. matrix i ; fraction j > LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j )  2% OR PEC1 matrix i ; fraction j  PEC2 matrix i ; fraction j ] High PEC2 matrix i ; fraction j / PNEC matrix i >10 AND PEC1 matrix i ; fraction j / PNEC matrix i >1 AND [ (nb anal. matrix i ; fraction j > LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j )  2% OR PEC1 matrix i ; fraction j  PEC2 matrix i ; fraction j ] Medium PEC2 matrix i ; fraction j / PNEC matrix i >1 AND PEC1 matrix i ; fraction j / PNEC matrix i >1 AND [ (nb anal. matrix i ; fraction j > LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j )  2% OR PEC1 matrix i ; fraction j  PEC2 matrix i ; fraction j ] Not applicable PEC2 matrix i ; fraction j / PNEC matrix i >10 AND [ (nb anal. matrix i ; fraction j >LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j ) < 2% OR PEC1 matrix i ; fraction j < PEC2 matrix i ; fraction j ] Low “Very high” = FALSE AND “High” = FALSE AND “Medium” = FALSE AND “Not applicable” = FALSE Prioritisation algorithm

12. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 12 Priority matrix i, fraction j Definition Very high PEC2 matrix i ; fraction j / PNEC matrix i >100 AND PEC1 matrix i ; fraction j / PNEC matrix i >1 AND [ (nb anal. matrix i ; fraction j > LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j )  2% OR PEC1 matrix i ; fraction j  PEC2 matrix i ; fraction j ] High PEC2 matrix i ; fraction j / PNEC matrix i >10 AND PEC1 matrix i ; fraction j / PNEC matrix i >1 AND [ (nb anal. matrix i ; fraction j > LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j )  2% OR PEC1 matrix i ; fraction j  PEC2 matrix i ; fraction j ] Medium PEC2 matrix i ; fraction j / PNEC matrix i >1 AND PEC1 matrix i ; fraction j / PNEC matrix i >1 AND [ (nb anal. matrix i ; fraction j > LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j )  2% OR PEC1 matrix i ; fraction j  PEC2 matrix i ; fraction j ] Not applicable PEC2 matrix i ; fraction j / PNEC matrix i >10 AND [ (nb anal. matrix i ; fraction j >LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j ) < 2% OR PEC1 matrix i ; fraction j < PEC2 matrix i ; fraction j ] Low “Very high” = FALSE AND “High” = FALSE AND “Medium” = FALSE AND “Not applicable” = FALSE Prioritisation algorithm See Annex XI of the report

13. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 13 Changes made in the prioritisation algorithm since march 2009 Reasons for changes : New data collection in 2009 (end in January 2009) From the 1 st stage ranking to the final process : 5 to 14.6 millions data Shift in quality : higher determination limits Impact in the algorithm

14. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 Distribution of determination limits The example of Cypermethrin Max of DL Data collection until October 2008

15. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 15 Priority matrix i, fraction j Definition Very high or High or Medium PEC2 matrix i ; fraction j / PNEC matrix i >100 (Very high) or 10 (High) or 1 (Medium) AND PEC1 matrix i ; fraction j / PNEC matrix i >1 AND [ (nb anal. matrix i ; fraction j > LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j )  2% OR PEC1 matrix i ; fraction j  PEC2 matrix i ; fraction j ] Changes made in the prioritisation algorithm since march 2009 Priority matrix i, fraction j Definition Very high or High or Medium PEC2 matrix i ; fraction j / PNEC matrix i >100 (Very high) or 10 (High) or 1 (Medium) AND PEC1 matrix i ; fraction j / PNEC matrix i >1 AND [ (nb anal. matrix i ; fraction j > LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j )  10% AND PEC1 matrix i ; fraction j  PEC2 matrix i ; fraction j ]

16. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 16 Priority matrix i, fraction j Definition Very high or High or Medium PEC2 matrix i ; fraction j / PNEC matrix i >100 (Very high) or 10 (High) or 1 (Medium) AND PEC1 matrix i ; fraction j / PNEC matrix i >1 AND [ (nb anal. matrix i ; fraction j > LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j )  2% OR PEC1 matrix i ; fraction j  PEC2 matrix i ; fraction j ] Changes made in the prioritisation algorithm since march 2009 Priority matrix i, fraction j Definition Very high or High or Medium PEC2 matrix i ; fraction j / PNEC matrix i >100 (Very high) or 10 (High) or 1 (Medium) AND PEC1 matrix i ; fraction j / PNEC matrix i >1 AND [ (nb anal. matrix i ; fraction j > LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j )  10% AND PEC1 matrix i ; fraction j  PEC2 matrix i ; fraction j ] 2%OR

17. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 17 Priority matrix i, fraction j Definition Not applicable [ PEC2 matrix i ; fraction j /PNEC matrix i >10 OR PEC2 matrix i ; fraction j /(90 th percent. bkg) matrix i >10 ] AND [ (nb anal. matrix i ; fraction j >DL matrix i ; fraction j )/(nb all anal. matrix i ; fraction j ) < 10% OR PEC1 matrix i ; fraction j < PEC2 matrix i ; fraction j ] Prioritisation algorithm : Label “Not applicable” priority Priority matrix i, fraction j Definition Not applicable [ PEC2 matrix i ; fraction j /PNEC matrix i >10 OR PEC2 matrix i ; fraction j /(90 th percent. bkg) matrix i >10 ] AND [ (nb anal. matrix i ; fraction j >DL matrix i ; fraction j )/(nb all anal. matrix i ; fraction j ) < 10% OR PEC1 matrix i ; fraction j < PEC2 matrix i ; fraction j ]

18. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 18 Priority matrix i, fraction j Definition Not applicable [ PEC2 matrix i ; fraction j /PNEC matrix i >10 OR PEC2 matrix i ; fraction j /(90 th percent. bkg) matrix i >10 ] AND [ (nb anal. matrix i ; fraction j >DL matrix i ; fraction j )/(nb all anal. matrix i ; fraction j ) < 10% OR PEC1 matrix i ; fraction j < PEC2 matrix i ; fraction j ] Prioritisation algorithm : Label “Not applicable” priority Priority matrix i, fraction j Definition Not applicable [ PEC2 matrix i ; fraction j /PNEC matrix i >10 OR PEC2 matrix i ; fraction j /(90 th percent. bkg) matrix i >10 ] AND [ (nb anal. matrix i ; fraction j >DL matrix i ; fraction j )/(nb all anal. matrix i ; fraction j ) < 10% OR PEC1 matrix i ; fraction j < PEC2 matrix i ; fraction j ] 2% OR No PNEC available OR No PEC1 available OR No PEC2 available

19. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 19 Prioritisation algorithm : Label “Not applicable” priority Priority matrix i, fraction j Definition Not applicable PEC2 matrix i ; fraction j / PNEC matrix i >10 AND [ (nb anal. matrix i ; fraction j >LoDet matrix i ; fraction j )/(nb all anal. matrix i ; fraction j ) < 2% OR PEC1 matrix i ; fraction j < PEC2 matrix i ; fraction j ] OR No PNEC available OR No PEC1 available OR No PEC2 available Priority matrix i, fraction j Definition Not applicable [ PEC2 matrix i ; fraction j /PNEC matrix i >10 OR PEC2 matrix i ; fraction j /(90 th percent. bkg) matrix i >10 ] AND [ (nb anal. matrix i ; fraction j >DL matrix i ; fraction j )/(nb all anal. matrix i ; fraction j ) < 10% OR PEC1 matrix i ; fraction j < PEC2 matrix i ; fraction j ]

20. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 20 Prioritisation algorithm : Label “Low” priority Priority matrix i, fraction j Definition Low “Very high” = FALSE AND “High” = FALSE AND “Medium” = FALSE AND “Not applicable” = FALSE “Low” : Not explicitly explained

21. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 At each level, the worst case is taken into account 21 Example at matrix level : Priority Sed 2mm = “Low” Priority Sed 20µm = “Not applicable” Priority Sed 63µm = “Low” resulting priority for sediment is “Not applicable” At each level, “Not applicable” label prevails on “Low” label Drinking water conclusions are taken into account separately Relation between Priority labels See Annex XI of the report

22. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 22 Risk ratios for PCBs 3 approaches: Ris k ratios based on data provided as “Total PCB” (i.e., in most cases, sum of 7 “standard” congeners) Risk ratios based on data for individual congeners (estimating PNEC of individual congeners from PNEC of total PCB) Risk ratios calculated by summing concentrations of all available congeners which are concomitantly measured at a given station (“Sum of PCB”) See Annex IX of the report risk is identified for PCB for all matrices

23. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 23 Risk ratios for dioxins/dioxin like compounds Summing TEFs of all dioxin like compounds (PCDDs, PCDFs, dl PCBs) concomitantly measured at a given station (“Sum of dioxins”) See Annex X of the report Risk detected for water, sediment biota and human health

24. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 COMMPS monitoring-based approach versus risk ratio monitoring-based approach COMMPS monitoring-based approach do not use monitoring data in biota Differences in the algorithm : Weight given to criteria : COMMPS monitoring-based approach provides more weight to direct effects (EFSd) than to secondary poisoning (EFSi) or protection of human health (EFSh) Risk-ratio based approach provides the same weight to all matrices taking into account for final results the worst case at any level of the prioritisation process. aggregation of exposure and effects indices in COMMPS, effect indices aggregating direct effects, secondary poisoning and human health are directly compared to exposure indices in aquatic phase or in sediment risk-ratio based approach compares effects with indices at each level (fractions and then matrices) 24

25. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 25 COMMPS monitoring-based approach 2009 versus 1999 Existing PS prioritised according to monitoring data in COMMPS 1999 would not necessarily be prioritised applying COMMPS to 2009 data set Rationale : change in PEC values and PNEC values PECwater (µg/l)PNECwater (µg/l) CASSubstanceName1999200919992009 1912-24-9Atrazine0.410.050.80.6 75-09-2Dichloromethane10.255111650 COMMPS 1999Monitoring-based COMMPS 2009 CASSubstanceName WFD EQSD PS COMMPS 1999 prioritisation based on monitoring Max [I_PRIOwater;I_PRIOsed] Rank 959-98-8Endosulfan - alphaXX113,671309835 1912-24-9AtrazineXX113,335253436 319-85-7Hexachlorocyclohexane - betaXX110,313460542 75-09-2DichloromethaneXX70,5181251887

26. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 26 COMMPS monitoring-based approach 2009 versus 1999 Existing PS prioritised according to monitoring data in COMMPS 1999 would not necessarily be prioritised applying COMMPS to 2009 data set Rationale : change in PEC values and PNEC values PECwater (µg/l)PNECwater (µg/l) CASSubstanceName1999200919992009 1912-24-9Atrazine0.410.050.80.6 75-09-2Dichloromethane10.255111650 COMMPS 1999Monitoring-based COMMPS 2009 CASSubstanceName WFD EQSD PS COMMPS 1999 prioritisation based on monitoring Max [I_PRIOwater;I_PRIOsed] Rank 959-98-8Endosulfan - alphaXX113,671309835 1912-24-9AtrazineXX113,335253436 319-85-7Hexachlorocyclohexane - betaXX110,313460542 75-09-2DichloromethaneXX70,5181251887

27. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 Results before review step ORGANICS 65 substances are prioritised as “Very high” or “High” priority substances (including 10 individual PCBs, “PCBs - 3 approaches”, “Sum of dioxins”) 21 of which are existing priority substances (PS) or isomers of existing PS METALS 8 substances are prioritised as “Very high” or “High” priority substances the 4 existing PS are prioritised “High” 27

28. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 Review of the results Check EU representativeness at the determinant fraction level : Nb country >= 3 for the fraction determining the final priority rank 28 MatrixPNEC AF for PNEC Fraction Nb country Nb RBD Nb stations Nb analysis > DL Nb all analysis Rank Final Rank Water (µg/L) 0,0002-Whole water42711106348900High Sediment (µg/kg dw) 0,2025EqP Sed 2mm2883587926High Sed 20µm1884179793High Sed 63 µm00000Not Applicable Biota (mg/kg food) -- Fish00000Not Applicable Invertebrates00000Not Applicable Ex of Tetrabutyltin compounds

29. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 Review of the results Check EU representativeness at the determinant fraction level : Nb country >= 3 for the fraction determining the final priority rank 29 Ex of Heptachlor epoxide MatrixPNEC AF For PNEC Fraction Nb country Nb RBD Nb stations Nb Analysis > LoDet Nb analysis Rank Final Rank Water (µg/L)0.000031000Whole water114715382912284Very high Sediment (µg/kg dw) 0.0159EqP Sed 2mm38881431047Very high Sed 20µm25100160Not Applicable Sed 63 µm12309Not Applicable Biota (mg/kg food) 0.000007- Fish11202Not Applicable Invertebrates23111320Very high

30. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 Review of the results 30 Check reliability of monitoring data : when DL > 2*PNEC, non quantified analysis not deemed reliable non quantified analysis with DL>2*PNEC are discarded PEC values are re calculated and risk is re evaluated MatrixFraction Before / after discard Nb countries Nb RBD Nb Analysis >LoDet Nb of total analysis PEC1PEC2Rank Final rank WaterWhole water before114729122840.121550.02Very high after41129740.121550.102565Very high SedimentSed 2mm before38431047399.17510Very high after2243 399.175 Very high Ex of Heptachlor epoxide

31. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 Results after review Apart from existing priority substances (Dir. 2008/105/EC) 41 substances are prioritised before review, including 34 organic substances, PCBs and dioxins and 4 metals 14 organic substances and the 4 metals are identified as candidates for deselection 31

32. International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 International Office for Water Alice James - WG E (6), Brussels, 6 July 2009 Conclusions and perspectives Some substances should be investigated by the modelling approach : Substances labelled “Not applicable” Substances deselected after review on the EU representativity criteria at fraction level 32 Further review on quality and representativeness should be performed