MODELKEY ( GOCE) is a research project funded by 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

MODELKEY ( GOCE) is a research project funded by ~ 50 mio known chemicals (CAS) Priority Substances (Chemical Status) Problem: too many chemicals  Need to prioritize chemicals River Basin Specific Substances (Ecological Status) 178

MODELKEY ( GOCE) is a research project funded by Compounds (>LoQ) AA-EQS Priority Substances  How to assess the others? AA-EQS River Basin Specific Total Quality Standards Elbe Danube Total Compounds measured MODELKEY + ICPDR databases

MODELKEY ( GOCE) is a research project funded by 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?

MODELKEY ( GOCE) is a research project funded by 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

MODELKEY ( GOCE) is a research project funded by 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)

MODELKEY ( GOCE) is a research project funded by ACF Similarity Threshold nr2r2 q2q2 rms 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: /es200361r Read-across: ACF-based Acute Fathead minnow Toxicity (96-h log LC50)

MODELKEY ( GOCE) is a research project funded by 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′

MODELKEY ( GOCE) is a research project funded by Lowest PNEC STD = standard test data RA = data from existing Risk Assessments

MODELKEY ( GOCE) is a research project funded by 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

MODELKEY ( GOCE) is a research project funded by SPEAR [%] Effect AF 1000 log TU Max Daphnia magna Von der Ohe et al. 2009, IEAM 5, LC50 P-PNEC: overly protective? sublethal concentrations! P- PNEC Toxic pressure

MODELKEY ( GOCE) is a research project funded by LC50 Chlorfenvinphos Von der Ohe et al. 2011, STOTEN 409, Mesocosm-based EQS: safe? Chlorpyrifos P- PNEC  sublethal exposure shapes the community! SPEAR [%] log TU Max Daphnia magna

MODELKEY ( GOCE) is a research project funded by 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

MODELKEY ( GOCE) is a research project funded by 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

MODELKEY ( GOCE) is a research project funded by 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

MODELKEY ( GOCE) is a research project funded by 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.

MODELKEY ( GOCE) is a research project funded by 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

MODELKEY ( GOCE) is a research project funded by Prioritization Results

MODELKEY ( GOCE) is a research project funded by 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

MODELKEY ( GOCE) is a research project funded by 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

MODELKEY ( GOCE) is a research project funded by Thank You!

MODELKEY ( GOCE) is a research project funded by

MODELKEY ( GOCE) is a research project funded by log EQS log P-PNEC Verification: P-PNEC vs EQS

MODELKEY ( GOCE) is a research project funded by 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

MODELKEY ( GOCE) is a research project funded by P-PNEC vs PNEC chronic log PNEC chronic log P-PNEC

MODELKEY ( GOCE) is a research project funded by P-PNEC vs PNEC chronic log P-PNEC log PNEC chronic NOEC = LC50 Acute to chronic ratio: NOEC is similar to the acute LC50

MODELKEY ( GOCE) is a research project funded by P-PNEC vs PNEC acute log P-PNEC log PNEC acute

MODELKEY ( GOCE) is a research project funded by Prioritization: Elbe English namePPAA-EQSP-PNECSourceBQEUse Class# of sitesFrequencyExceedance azoxystrobin0.1060LApesticide18187%>1000 dioctyltin0.0001PFbiocide13899%>100 terbutylazine LApesticide71081%>100 perfluorooctanoate0.0029PMindustrial baseproduct1493%>10 2,4'-DDT0.0048LMpesticide19873%>10 indeno(1,2,3-c,d)pyrene PFcombustion product53972%>10 diuron LApesticide21969%>10 4,4'- DDT LMpesticide40068%>10 irgarol LApesticide26037%>100 terbutryne LApesticide45065%>10 benzo[b]fluoranthene PFcombustion product63255%>10 HHCB (Galaxolide®)0.0380LMindustrial baseproduct78859%>1 metolachlor LApesticide30146%>10 alachlor LApesticide7944%>10 flufenacet0.0035LApesticide18340%>10 benzo[k]fluoranthene PFcombustion product58539%>10 ametryne LApesticide2548%>1 hexazinon LApesticide8137%>10 prometryn LApesticide18446%>1 cyanazine0.0224LApesticide1644%>1 dimethenamid0.0180LApesticide1942%>1 desethylterbutylazine0.0154PApesticide27139%>1 malathion LMpesticide2335%>1 desphenyl-chloridazon0.0626PApesticide3631%>1 4-nonylphenol (tech) LFindustrial baseproduct62726%>1 benzo[ghi]perylene PMcombustion product52125%>1 chlorphyriphos-ethyl0.0013LMpesticide62323%>1 AHTN (Tonalide®)0.0303PMindustrial baseproduct48022%>1 dimetachlor0.0298PApesticide15722%>1 parathion-ethyl LMpesticide1921%>1 pirimicarb LMpesticide8320%>1

MODELKEY ( GOCE) is a research project funded by Prioritization: Danube english namePPAA-EQSP-PNECSourceBQEUse Class# of sitesFrequencyExceedance alachlor LApesticide23100%>100 4,4'- DDT LMpesticide24100%>10 metolachlor LApesticide23100%>10 4,4'- DDD0.0373PMpesticide23100%>10 simazine LApesticide3861%>100 perfluorononanoate0.0004PMindustrial baseproduct61100%>1 terbutylazine LApesticide8783%>10 aldrin PMpesticide2882%>10 4,4'- DDE0.0301PMpesticide2391%>1 b-hexachlorocyclohexane0.0820LFpesticide2387%>1 endosulfan II LMpesticide2383%>1 perfluorooctanoate0.0029PMindustrial baseproduct9671%>10 endrin LMpesticide2871%>1 diuron LApesticide6070%>1 endosulfan I LMpesticide2365%>1 lindane LFpesticide2864%>1 methoxychlor0.0528LMpesticide1450%>1 heptachlor PApesticide3047%>1 dieldrin LMpesticide2825%>1 a-hexachlorocyclohexane0.0820LFpesticide2322%>1 atrazine LApesticide12819%>1 desethylterbutylazine0.0154PApesticide8514%>1 nonylphenol-1-carboxylate0.1759PFindustrial baseproduct10314%>1 benzo[k]fluoranthene PFcombustion product157%>1 fluoranthene LFindustrial intermidiate356%>1 perfluorooctansulfonate0.0271PFindustrial baseproduct984%>1 desethylatrazine0.0308PApesticide913%>1