1. 15-16 March 2010, WG-E, DG-ENV, Brussels1 Results of the modelling-based prioritisation exercise J.M. Zaldívar, K. Daginnus, S. Gottardo and A. Payá Institute for Health and Consumer Protection Joint Research Centre, European Commission H. Wilkinson and P. Whitehouse Environment Agency, UK Expert group on Review of WFD Priority Substances List http://ecb.jrc.ec.europa.eu/qsar/

2. 15-16 March 2010, WG-E, DG-ENV, Brussels2 OUTLINE Introduction Identification of candidates for prioritisation Process overview Preliminary screening Hazard assessment - Persistence - Bioaccumulation - Toxicity Exposure Assessment Final Ranking PNEC estimation PEC estimation - ECETOC TRA Tool - Multimedia modelling Results Conclusions Next Steps

3. 15-16 March 2010, WG-E, DG-ENV, Brussels3 INTRODUCTION Outline of the prioritisation approach (two steps): - Screening (2034 compounds) - Ranking (78 compounds)

4. 15-16 March 2010, WG-E, DG-ENV, Brussels4 Starting list of Chemicals Updated list agreed on last meeting (15/9/09) after the addition of proposals from: EEB, Greenpeace, TC-NES PBT working group, EU endocrine disruptors database (lists 1 & 2, DG-ENV), OSPAR, Joint Danube Survey and NORMAN to the existing list proposed by JRC. CAS merge: 2034 substances.

5. 15-16 March 2010, WG-E, DG-ENV, Brussels5 Screening: Hazard Assessment P stands for Persistent (0/1) B= Bioaccumulative (0/1) T=Toxic (0/1) ED = priority list of Endocrine disruptors Cat. 1 and 2 (0/1) modified from Wilkinson et al. (2007)

6. 15-16 March 2010, WG-E, DG-ENV, Brussels6 Screening: Exposure Assessment modified from Wilkinson et al. (2007) Exposure scoreDefinition 0Annual use: 0-1 tons 1Annual use: 1-10 tons 2Annual use: 10-100 tons 3Annual use: 100-1000 tons 4Annual use: >1000 tons ContributionIndexApproach A. How much is produced/ imported annually in EU? Ton/yearData from IUCLID and SPIN (Nordic Countries) databases B. What is the use pattern?Use Index (0.1-1) A factor is applied to Ton/year based on use pattern: 0.1 Controlled system (isolated intermediate) 0.2 Industrial (non dispersive) use or use resulting in inclusion into/onto matrix 0.5 Wide dispersive use (mainly diffusive sources) 1.0 Used in the environment

7. 15-16 March 2010, WG-E, DG-ENV, Brussels7 Screening: Risk (Hazard & Exposure) Assessment Exposure assessment score Hazard Assessment score 43210 411235 312235 222345 133445 055555 First stepSecond step Only for substances with value 1 - PEC estimation - PNEC estimation - Risk ratio=PEC/PNEC modified from Wilkinson et al. (2007)

8. 15-16 March 2010, WG-E, DG-ENV, Brussels8 Hazard Assessment: Persistence (Screening) - P screening: BIOWIN or BIOHCWIN (EPI suite TM ) - vP screening: OECD P ov and LRTP screening tool 13.2% 33.1% 53.7%

9. 15-16 March 2010, WG-E, DG-ENV, Brussels9 BCF values (Arnot BCF and Footprint databases) QSAR, EPI Suite (BCFBAF),CAESAR bioaccumulation and JRC tool (error ~ 0.5 log units) Hazard Assessment: Bioaccumulation (Screening)

10. 15-16 March 2010, WG-E, DG-ENV, Brussels10 Hazard Assessment: Toxicity (Screening) Footprint (NOECs, EC50 pesticides), ECETOC (NOECs, EC50) DSSTOX (EC50) data- mined for experimental data 4 QSAR models (ADMET Predictor proprietary model, 3 JRC models) were run to estimate toxicity using a consensus approach

11. 15-16 March 2010, WG-E, DG-ENV, Brussels11 Exposure Assessment (Screening) An algorithm to extract data from IUCLID was implemented (http://iuclid.echa.europa.eu/) as well as data from SPIN 1 (http://www.spin2000.net/) provided. Use and type of use of substances from IUCLID (if several uses maximum value was chosen) Problems: IUCLID has old data, data for 56% compounds not found 1 SPIN (Substances in preparations in Nordic countries) is a database on the use of Substances in Products in the Nordic Countries. The database is based on data from the Product Registries of Norway, Sweden, Denmark and Finland. The database is financed by the Nordic Council of Ministers, Chemical group.

12. 15-16 March 2010, WG-E, DG-ENV, Brussels12 Screening results 78 compounds classified with Risk Score 1 Next step, Ranking: Obtain a risk ratio (PEC/PNEC) for these compounds relevant databases for Toxicity and PNEC estimation PEC estimation

13. 15-16 March 2010, WG-E, DG-ENV, Brussels13 PNEC Estimation (Ranking) PNECs were calculated with preference for experimental data over QSAR and NOEC over EC 50. Several databases were mined to find toxicological data, When no PNEC was accessible, the data were combined in a developed algorithm to estimate a value for each specific compound. In case of data gaps and when a QSAR estimation was applied provisional PNECs were calculated using the mean of the predicted EC 50 from the 4 modules and the assessment factor (AF) 1000.

14. 15-16 March 2010, WG-E, DG-ENV, Brussels14 Proposed application to estimate PEC/PNEC ratio for substances with risk score = 1 ECETOC has developed a tiered approach for calculating the exposure and related risks to consumers, workers and the environment caused by chemicals implementing REACH Guidance:  Tier 1: based on pre-defined and conservative use scenarios corresponding to Environmental Release Categories (ERC) described under REACH Guidance (Chapter R.16)  Tier 2: detailed risk assessment on previously identified uses (additional more realistic exposure input) Developed in Excel, contains the user interface and the datasheets Freely downloadable after registration from: http://www.ecetoc.org/tra PEC Estimation: ECETOC TRA tool (Ranking)

15. 15-16 March 2010, WG-E, DG-ENV, Brussels15 PEC Estimation: Multimedia modelling (Ranking) from REACH Guidance Distribution in water from OECD LRTP: Alachlor (example): Emission to air: Pov = 64 days; CDT = 90 km; Emission to water: Pov = 173 days; CDT = 298 km; Emission to soil: Pov = 328 days; Overall: Pov = 328 days CDT = 298 km. Distribution in water (equilibrium) = 98.86% Pov (Overall Persistence) CDT (Characteristic Travel Distance) http://www.oecd.org/env/riskassessment

16. 15-16 March 2010, WG-E, DG-ENV, Brussels16 PEC calculation: ECETOC- Multimedia - Good agreement for wide dispersive chemicals - ECETOC gave too high values for non dispersive chemicals - Solubility is required in ECETOC but not considered for PEC

17. 15-16 March 2010, WG-E, DG-ENV, Brussels17 RANKED RESULTS (Top 20) CASName 2921-88-2chlorpyrifos 834-12-8ametryn (ECPA-S: not used anymore in EU) 1085-98-9Dichlofluanide 7287-19-6prometryn (ECPA-S: not used anymore in EU) 55283-68-6ethalfluralin 886-50-0terbutryn (ECPA-S: modelling PNEC values lower) 52315-07-8alpha-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylate 5598-13-0chlorpyrifos-methyl (DAS: low production, PEC, PNEC values) 42576-02-3methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate 118-82-12,2',6,6'-tetra-tert-butyl-4,4'-methylenediphenol (TBMD) (CEFIC: Tonnage lower) 1897-45-6chlorothalonil (ECPA-S: modelling PNEC values lower, biodegradable) 79-94-72,2',6,6'-tetrabromo-4,4'-isopropylidenediphenol (RAR concern aquatic compartment: yes) 1582-09-8trifluralin (DAS: PEC, PNEC values) 107-64-2Dimethyldioctadecylammonium chloride (RAR concern aquatic compartment: no) 74070-46-52-chloro-6-nitro-3-phenoxyaniline 2312-35-8propargite 77-47-4hexachlorocyclopentadiene (RAR concern aquatic compartment: no) 67747-09-5N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]-1H-imidazole-1-carboxamide 115-32-2Dicofol 1861-40-1benfluralin

18. 15-16 March 2010, WG-E, DG-ENV, Brussels18 Comments from Chem. Industry New production levels for 3 compounds New Physico-chem. properties for one compound PEC/PNEC risk ratio recalculated for these compounds

19. 15-16 March 2010, WG-E, DG-ENV, Brussels19 RANKED RESULTS (Top 20) After comments from Chem. Ind. CASName 2921-88-2 chlorpyrifos 834-12-8 ametryn 1085-98-9 Dichlofluanide 7287-19-6 prometryn 55283-68-6 ethalfluralin 886-50-0 terbutryn 52315-07-8 alpha-cyano-3-phenoxybenzyl 3-(2,2-dichlorovinyl)-2,2 dimethylcyclopropanecarboxylate 42576-02-3 methyl 5-(2,4-dichlorophenoxy)-2-nitrobenzoate 1897-45-6 chlorothalonil 79-94-7 2,2',6,6'-tetrabromo-4,4'-isopropylidenediphenol 1582-09-8 trifluralin 107-64-2 Dimethyldioctadecylammonium chloride 74070-46-5 2-chloro-6-nitro-3-phenoxyaniline 2312-35-8 propargite 77-47-4 hexachlorocyclopentadiene 67747-09-5 N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]-1H-imidazole-1-carboxamide 115-32-2 Dicofol 50-29-3 clofenotane 5102-83-0 2,2'-[(3,3'-dichloro[1,1'-biphenyl]-4,4'-diyl)bis(azo)]bis[N-(2,4-dimethylphenyl)-3-oxobutyramide] 5468-75-7 2,2'-[(3,3'-dichloro[1,1'-biphenyl]-4,4'-diyl)bis(azo)]bis[N-(2-methylphenyl)-3-oxobutyramide]

20. 15-16 March 2010, WG-E, DG-ENV, Brussels20 CONCLUSIONS  A model-based approach for chemical prioritization under the WFD has been developed  Two phases: First screening (2034 compounds) and second PEC/PNEC estimation (78 compounds)  Positive points: Complements monitoring data (no use of the database developed by the monitoring approach)  Drawbacks: Estimated data and properties (PBT assessment possible for 76%), hard to find data on production levels (46% compounds) and use assessment, no data on emissions (eg. chemicals produced by combustion), PEC/PNEC uncertain (only for internal ranking).

21. 15-16 March 2010, WG-E, DG-ENV, Brussels21 NEXT STEPS  Short term:  Combining lists (DG-ENV proposal)  Expert review  Replacement of estimated data/parameters by experimental values for finally selected compounds (Dossiers)  Long term:  Develop an workflow task/package for subsequent prioritisation exercises (open source tool) that is accessible to all interested parties

22. 15-16 March 2010, WG-E, DG-ENV, Brussels22 RANKED RESULTS (Top 20) Score CASName 21 50-29-3clofenotane 22 5102-83-02,2'-[(3,3'-dichloro[1,1'-biphenyl]-4,4'-diyl)bis(azo)]bis[N-(2,4-dimethylphenyl)-3-oxobutyramide] 23 5468-75-72,2'-[(3,3'-dichloro[1,1'-biphenyl]-4,4'-diyl)bis(azo)]bis[N-(2-methylphenyl)-3-oxobutyramide] 24 1120-36-1Tetradecene 25 96-69-56,6'-di-tert-butyl-4,4'-thiodi-m-cresol 26 63449-39-8Paraffin waxes and Hydrocarbon waxes, chloro (LCCP) (CEFIC:not PBT/vPvB) 27 52-68-6trichlorfon 28 1912-24-9atrazine 29 2082-79-3octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate 30 119-47-16,6'-di-tert-butyl-2,2'-methylenedi-p-cresol 31 2303-17-5tri-allate 32 56-35-9bis(tributyltin) oxide 33 6683-19-8 3-{[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]oxy}-2,2-bis({[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoyl]oxy}methyl)propyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propanoate 34 120-82-11,2,4-trichlorobenzene (RAR concern aquatic compartment: yes) 35 731-27-1N-{[dichloro(fluoro)methyl]sulfanyl}-N',N'-dimethyl-N-(4-methylphenyl)sulfuric diamide (ECPA-S: Lower tonnage) 36 4979-32-2N,N-dicyclohexylbenzothiazole-2-sulphenamide 37 67774-74-7undecylbenzene (RAR concern aquatic compartment: no) 38 32534-81-9diphenyl ether, pentabromo derivative 39 68442-68-24-(1-phenylethyl)-N-[4-(1-phenylethyl)phenyl]aniline 40 135-91-14,4'-methylenebis[N,N-diethylaniline] 41 31570-04-4tris(2,4-ditert-butylphenyl) phosphite 42 5567-15-72,2'-[(3,3'-dichloro[1,1'-biphenyl]-4,4'-diyl)bis(azo)]bis[N-(4-chloro-2,5-dimethoxyphenyl)-3-oxobutyramide] 43 64131-85-7O,O,O-tris(4-nitrophenyl) thiophosphate 44 294-62-2cyclododecane (CEFIC: not SVHC) 45 25637-99-4hexabromocyclododecane (RAR concern aquatic compartment: yes) 46 3194-55-6 1,2,5,6,9,10-hexabromocyclodecane (RAR concern aquatic compartment: yes) 47 732-26-32,4,6-tri-tert-butylphenol 48 118-74-1Hexachlorobenzene 49 5915-41-3terbuthylazine 50 5216-25-1alpha,alpha,alpha,4-tetrachlorotoluene 51 52740-90-61-amino-N-(3-bromo-9,10-dihydro-9,10-dioxo-2-anthryl)-9,10-dihydro-9,10-dioxoanthracene-2-carboxamide 52 3861-47-04-cyano-2,6-diiodophenyl octanoate 53 21850-44-21,1'-(isopropylidene)bis[3,5-dibromo-4-(2,3-dibromopropoxy)benzene] 54 470-90-6chlorfenvinphos 55 1163-19-5Bis(pentabromophenyl) ether (RAR concern aquatic compartment: no) 56 60207-90-11-[[2-(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]-1H-1,2,4-triazole (ECPA-S: no risk aquatic environment) 57 87-68-3hexachlorobuta-1,3-diene 58 13356-08-6bis(tris(2-methyl-2-phenylpropyl)tin) oxide 59 25103-58-6tert-dodecanethiol 60 32536-52-0diphenyl ether, octabromo derivative (RAR concern aquatic compartment: no) 61 629-59-4tetradecane 62 38521-51-62,3,4,5,6,alpha-hexabromotoluene 63 101-05-3Anilazine 64 1461-25-2tetrabutyltin (TTBT) (CEFIC: intermediate, minimum release) 65 21725-46-2cyanazine 66 122-34-9simazine 67 31565-23-8di(tert-dodecyl) pentasulphide 68 61213-25-03-chloro-4-(chloromethyl)-1-[3-(trifluoromethyl)phenyl]pyrrolidin-2-one 69 93-46-9N,N'-di-2-naphthyl-p-phenylenediamine 70 84852-53-91,1'-(ethane-1,2-diyl)bis[pentabromobenzene] 71 52434-90-91,3,5-tris(2,3-dibromopropyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione 72 13680-35-84,4'-methylenebis[2,6-diethylaniline] 73 469-61-4[3R-(3alpha,3abeta,7beta,8aalpha)]-2,3,4,7,8,8a-hexahydro-3,6,8,8-tetramethyl-1H-3a,7-methanoazulene 74 133-49-3pentachlorobenzenethiol 75 3520-72-74,4'-[(3,3'-dichloro[1,1'-biphenyl]-4,4'-diyl)bis(azo)]bis[2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one] 76 1222-05-54,6,6,7,8,8-hexamethyl-1,3,4,6,7,8-hexahydrocyclopenta[g]isochromene (RAR concern aquatic compartment: no) 77 81-15-25-tert-butyl-2,4,6-trinitro-m-xylene 78 128-69-8isochromeno[4',5',6':6,5,10]anthra[2,1,9-def]isochromene-1,3,8,10-tetrone