1. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Prioritisation of potential river basin specific pollutants in four European river basins using MODELKEY and ICPDR databases Peter C. von der Ohe, Valeria Dulio, Jaroslav Slobodnik and Werner Brack

2. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org ~ 50 mio known chemicals (CAS) 33 + 8 Priority Substances (Chemical Status) Problem: too many chemicals  Need to prioritize chemicals River Basin Specific Substances (Ecological Status) 178

3. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org 233 87 Compounds (>LoQ) AA-EQS 42 31 Priority Substances 33 + 8  How to assess the others? AA-EQS 104 13 River Basin Specific Total 146 44 Quality Standards Elbe Danube Total 272 91 Compounds measured MODELKEY + ICPDR databases

4. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Risk Assessment Risk Assessment: Hazardous Quotient = PEC / PNEC Exposure Assessment: Predicted Environmental Concentration (PEC) Effect Assessment: Predicted No-Effect Concentration (PNEC)  No data, No problem?

5. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org micro-algae (Selenastrum capricornutum) invertebrates (Daphnia magna) fish (Pimephales promelas) ~550 tests ~ 1100 tests ~ 700 tests P-PNEC: provisional ′EQS′  predict missing data with read-across models

6. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Example: Phenylacetic acid ACFs: 5 · C aro H 1 (~C aro ) 2 1 · C aro H 0 (~C aro ) 2 (–C non-aro ) 1 · C non-aro H 2 (~C aro )(–C non-aro ) 1 · C non-aro H 0 (–O non-aro ) (=O non-aro )(–C non-aro ) 1 · O non-aro H 0 (=C non-aro ) 1 · O non-aro H 1 (–C non-aro ) OH O Atom-Centered Fragments (ACF)

7. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org ACF Similarity Threshold nr2r2 q2q2 rms 0.06920.730.720.73 0.75700.78 0.64 0.84190.78 0.61 0.853300.790.770.60 0.92300.87 0.43 n= number of valid resultsrms= root mean squared error r 2 = squared correlation coefficientq 2 = predictive squared corr. coeff. Schüürmann et al., EST 2011 DOI:10.1021/es200361r Read-across: ACF-based Acute Fathead minnow Toxicity (96-h log LC50)

8. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Step 2: Select lowest effect value (existing or predicted) Step 3: Select safety-factor (1000 on lowest acute value) EQS / P-PNEC Effect threshold Safety factor Toxic stress Effect Algae Invertebrate Fish Species-Sensitivity Distribution Step 1: Predict missing effect data (acute LC50) P-PNEC: provisional ′EQS′

9. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Lowest PNEC STD = standard test data RA = data from existing Risk Assessments

10. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Why lowest PNEC? Chronic data from three trophic levels: AF 10 Acute to Chronic ratio: chronic generally a factor 10 ACR 10 * AF 10 = 100x below the LC50 compared to 1000x  lowest PNEC value to be sure! This is less protective than acute PNEC, but not nescessarily less uncertain, because: Test species not the most sensitive ones Test durations in chronic tests are still to “short” Interaction between species are not considered

11. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org SPEAR [%] Effect AF 1000 log TU Max Daphnia magna - 4- 3- 2- 10 0 20 40 60 80 Von der Ohe et al. 2009, IEAM 5, 50-61 LC50 P-PNEC: overly protective? sublethal concentrations! P- PNEC Toxic pressure

12. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org LC50 Chlorfenvinphos Von der Ohe et al. 2011, STOTEN 409, 2064-2077 Mesocosm-based EQS: safe? - 4- 3- 2- 10 0 20 40 60 80 Chlorpyrifos P- PNEC  sublethal exposure shapes the community! SPEAR [%] log TU Max Daphnia magna

13. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org 13 Arithmetic mean 1 90 th percentile of all measures of all stations for : - A given substance - A given analytical fraction Raw data for: - A given substance - A given analytical fraction - A given station - At a given time station 2 station 1 station 3 Arithmetic mean 3 Arithmetic mean 2 Arithmetic means of all measures for : - A given substance - A given analytical fraction - A given station PECwater See Fribourg-Blanc (2008) Selection of manageable list = substances monitored by more than 3 countries INERIS proposal for calculation of PECs

14. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org 14 Criticism on the INERIS proposal Taking the average per site and compound will underestimate the exposure risk of discontinuous pollutants (e.g. pesticides)  take the maximum in consideration (95 th percenile) Taking the 90th percentile of all measured concentrations into consideration may overlook the really bad guys  take at least the 95 th percentile  considered for new prioritization approach

15. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Cat.Current situationAction needed 1There is already sufficient evidence on exposure and effects to prioritise them. EQS derivation and inclusion in routine monitoring programmes 2First evidence of occurrence in hazardous concentrations in the environment is available (e.g. field studies from research projects), but only few observations. Screening studies to inform about the current exposure situation 3These compounds were measured in the environment and are suspected to have effects on ecosystems and human health, but hazard assessment is based on predicted toxicity (P-PNEC) Perform rigorous hazard assessment 4For these compounds hazard assessment is based on experimental data, but observations in the environment are scarce (analytical capabilities not yet satisfactory). Improved analytical methods should be developed and validated 5These compounds have no or few observations in the environment and hazard assessment is based on predicted toxicity (P-PNEC). Screening studies and perform a rigorous hazard assessment 6Toxicity data is sufficient for the derivation of an EQS and there is evidence that the exposure does not pose a hazard to ecosystem and human health. Monitoring efforts for these compounds could be reduced. Six Action-categories

16. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org No Sufficient effect data? Yes No Monitoring database Cat. 3: Action ecotox Risk: MEC 95 > lowest PNEC? Analytical performance sufficient? LOQ < lowest PNEC? Yes Cat. 1: Candidates ecological status Cat. 6: not priority for monitoring Cat. 4: Action analytical Cat. 5: Action monitoring + ecotox Sufficient effect data? Yes Cat. 2: Action monitoring Yes Evidence of exposure at more than 20 water sites with analysis > LOQ All observations <LOQ Novel endpoints Classifcation into Action Categ.

17. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org 1 Frequenzy of exceedance of (P)-PNEC based on maximum concentrations per site (MEC site ) Indicators for Prioritization 2 Maximum exceedance of the 95 th percentile concentration of all sites (MEC 95 / (P)-PNEC)  Spatial distribution of potential effects  Extent of potential effects  Overall Ranking

18. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Prioritization Results

19. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Conclusions Organic chemicals may play an important role in ecological status deterioration Pesticides are among the most frequent and problematic compounds Prioritized compounds without experimental data should be tested Potentially problematic compounds with insufficient monitoring need more attention

20. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Recommendations Point source inputs (e.g. WWTP) of some substances should be considered in future River Basin Management Plans Measures that reduce run-off and drainage inputs from agriculture (soil erosion, nutrients and especially pesticides) should be favored! Monitoring programs should consider the intermittent release and peak concentrations of pesticides presently applied

21. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Thank You! peter.vonderohe@ufz.de

22. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org

23. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org -5 -3 1 3 5 -5-3135 log EQS log P-PNEC Verification: P-PNEC vs EQS

24. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org -5 -3 1 3 5 -5-3135 log EQS log P-PNEC Verification: P-PNEC vs EQS Second. poisoning NOEC = LC50 EQS ~ LC50 EQS value based on Mesocosm studies. PNEC in the range of acute LC50 Acute to chronic ratio: NOEC is similar to the acute LC50 Poisoning of predators: toxicity is difficult to predict

25. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org P-PNEC vs PNEC chronic -5 -3 1 3 5 -5-3135 log PNEC chronic log P-PNEC

26. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org P-PNEC vs PNEC chronic -5 -3 1 3 5 -5-3135 log P-PNEC log PNEC chronic NOEC = LC50 Acute to chronic ratio: NOEC is similar to the acute LC50

27. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org P-PNEC vs PNEC acute -5 -3 1 3 5 -5-3135 log P-PNEC log PNEC acute

28. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Prioritization: Elbe English namePPAA-EQSP-PNECSourceBQEUse Class# of sitesFrequencyExceedance azoxystrobin0.1060LApesticide18187%>1000 dioctyltin0.0001PFbiocide13899%>100 terbutylazine0.50.0032LApesticide71081%>100 perfluorooctanoate0.0029PMindustrial baseproduct1493%>10 2,4'-DDT0.0048LMpesticide19873%>10 indeno(1,2,3-c,d)pyrene280.0020.0013PFcombustion product53972%>10 diuron130.20.0024LApesticide21969%>10 4,4'- DDT340.010.0048LMpesticide40068%>10 irgarol0.0020.0014LApesticide26037%>100 terbutryne0.030.0059LApesticide45065%>10 benzo[b]fluoranthene280.030.0038PFcombustion product63255%>10 HHCB (Galaxolide®)0.0380LMindustrial baseproduct78859%>1 metolachlor0.20.0284LApesticide30146%>10 alachlor10.30.0045LApesticide7944%>10 flufenacet0.0035LApesticide18340%>10 benzo[k]fluoranthene280.030.0047PFcombustion product58539%>10 ametryne0.50.0042LApesticide2548%>1 hexazinon0.070.0068LApesticide8137%>10 prometryn0.50.0162LApesticide18446%>1 cyanazine0.0224LApesticide1644%>1 dimethenamid0.0180LApesticide1942%>1 desethylterbutylazine0.0154PApesticide27139%>1 malathion0.020.0148LMpesticide2335%>1 desphenyl-chloridazon0.0626PApesticide3631%>1 4-nonylphenol (tech)240.30.1384LFindustrial baseproduct62726%>1 benzo[ghi]perylene280.0020.0071PMcombustion product52125%>1 chlorphyriphos-ethyl0.0013LMpesticide62323%>1 AHTN (Tonalide®)0.0303PMindustrial baseproduct48022%>1 dimetachlor0.0298PApesticide15722%>1 parathion-ethyl0.0050.0020LMpesticide1921%>1 pirimicarb0.090.0167LMpesticide8320%>1

29. MODELKEY (511237-GOCE) is a research project funded by http://www.modelkey.org Prioritization: Danube english namePPAA-EQSP-PNECSourceBQEUse Class# of sitesFrequencyExceedance alachlor10.30.0045LApesticide23100%>100 4,4'- DDT340.010.0048LMpesticide24100%>10 metolachlor0.20.0284LApesticide23100%>10 4,4'- DDD0.0373PMpesticide23100%>10 simazine2910.1813LApesticide3861%>100 perfluorononanoate0.0004PMindustrial baseproduct61100%>1 terbutylazine0.50.0032LApesticide8783%>10 aldrin350.010.0451PMpesticide2882%>10 4,4'- DDE0.0301PMpesticide2391%>1 b-hexachlorocyclohexane0.0820LFpesticide2387%>1 endosulfan II140.0050.2432LMpesticide2383%>1 perfluorooctanoate0.0029PMindustrial baseproduct9671%>10 endrin370.010.1876LMpesticide2871%>1 diuron130.20.0024LApesticide6070%>1 endosulfan I140.0050.2432LMpesticide2365%>1 lindane180.020.0820LFpesticide2864%>1 methoxychlor0.0528LMpesticide1450%>1 heptachlor0.10.0327PApesticide3047%>1 dieldrin360.010.1876LMpesticide2825%>1 a-hexachlorocyclohexane0.0820LFpesticide2322%>1 atrazine30.60.1427LApesticide12819%>1 desethylterbutylazine0.0154PApesticide8514%>1 nonylphenol-1-carboxylate0.1759PFindustrial baseproduct10314%>1 benzo[k]fluoranthene280.030.0047PFcombustion product157%>1 fluoranthene150.10.0310LFindustrial intermidiate356%>1 perfluorooctansulfonate0.0271PFindustrial baseproduct984%>1 desethylatrazine0.0308PApesticide913%>1