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DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Chemical screening of pesticides through risk identification methods Dr.

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Presentation on theme: "DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Chemical screening of pesticides through risk identification methods Dr."— Presentation transcript:

1 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Chemical screening of pesticides through risk identification methods Dr. Frank Sacher DVGW-Technologiezentrum Wasser (TZW), Karlsruhe

2 Twinning Project PL06/IB/EN/01 Introduction Selection of target pesticides Practical examples from Germany Announcement of the German Health Authority Saarland lists NRW list TZW lists Example from Baden-Württemberg: The groundwater data base Pesticide metabolites Summary Outline

3 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Council Directive 98/83/EC on the quality of water intended for human consumption ANNEX I, Part B: Chemical parameters Parameter Parametric value UnitNotes Pesticides0.10µg/lNotes 6 and 7 Pesticides - Total0.50µg/lNotes 6 and 8

4 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Council Directive 98/83/EC on the quality of water intended for human consumption Note 6: Pesticides means: -organic insecticides -organic herbicides -organic fungicides -organic nematocides -organic acaricides -organic algicides -organic rodenticides -organic slimicides -related products (e.g. growth regulators) and their relevant metabolites, degradation and reaction products. Only those pesticides which are likely to be present in a given supply need to be monitored.

5 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Council Directive 98/83/EC on the quality of water intended for human consumption Note 7: The parametric value applies to each individual pesticide. In the case of aldrin, dieldrin, heptachlor and heptachlor epoxide the parametric value is µg/l. Note 8: Pesticides – Total means the sum of all individual pesticides detected and quantified in the monitoring procedure. No information included about which pesticides have to be monitored!!!

6 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Chemical structures of pesticides

7 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Degradation scheme of atrazine

8 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Standardized analytical methods for pesticides EN ISO Determination of plant treatment agents using HPLC with UV detection after solid-liquid extraction DIN EN ISO Determination of organic nitrogen and phosphorous compounds by gas chromatography DIN 38407, part 14 (F14) Determination of phenoxyalkanoic acids by GC/MSD after solid-phase extraction and derivatisation ISO Determination of selected phenoxyalkanoic herbicides, including bentazone and hydroxybenzonitriles by GC/MS after solid-phase extraction and derivatisation with diazomethane DIN 38407, part 11 (F11) Determination of organic pesticides by automated- multiple-development technique (AMD) DIN 38407, part 22 (F22) Determination of glyphosate and AMPA by HPLC, post- column derivatisation and fluorescence detection

9 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Council Directive 98/83/EC on the quality of water intended for human consumption ANNEX III, Part 2: Parameters for which performance characteristics are specified ParameterTrueness*Precision*LOD*ConditionsNotes Pesticides25 Note 6 * as % of parametric value Note 6: The performance characteristics apply to each individual pesticide and will depend on the pesticide concerned. The limit of detection may not be achievable for al pesticides at present, but Member States should strive to achieve this standard.

10 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Pesticides in raw waters for drinking water production Source: J. Kiefer & S. Sturm: Final report for research project W 1/02/05 Based on data from 477 water utilities

11 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Source: J. Kiefer & S. Sturm: Final report for research project W 1/02/05 Pesticides in raw waters for drinking water production

12 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Source: J. Kiefer & S. Sturm: Final report for research project W 1/02/05 Pesticides in raw waters for drinking water production

13 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Selection of target pesticides - Analytical limitations - Limitations of costs Large variety of pesticides that might occur in source waters Limited information on pesticide use in catchment area

14 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Decision on target list(s) for pesticides is made either by the health authorities (on different levels) the water utilities, or the laboratories that perform the analyses Decisions are made on federal or local level some Federal States have official lists (e.g. Saarland, NRW,…) sometimes local lists exist Only in few cases the target lists are based on land use or application of pesticides in the catchment area In most cases, target lists are based on analytical methods Practical strategies in Germany

15 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Example for lists of target pesticides: BGA List (1986) Table 1: 1. Aldicarb12. Isoproturon 2. Atrazin13. MCPA 3. Bentazon 14. Mecoprop 4. Bromacil15. Metazachlor 5. Chloridazon 16. Methabenzthiazuron 6. Chlortoluron 17. Metobromuron 7. Clopyralid 18. Metolachlor 8. 1,2-Dichlorpropan19. Metoxuron 9. 1,3-Dichlorpropen20. Propazin 10. Diuron21. Simazin 11. Endosulfan 22. Terbuthylazin Table 2 (optional): 23. Alachlor 24. Amitrol 25. Azinphos-ethyl 26. Carbofuran 27. Chlorfenvinphos 28. 2,4-D 29. Dicamba 30. Dichlobenil 31. Dichlorprop 32. Hexazinon 33. Lindan 34. Monuron 35. Parathion 36. Pyridat

16 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Example for lists of target pesticides: Saarland lists Corn: Glyphosat, AMPA, Isoproturon, Diflufenican, Florasulam, Pendimethalin, Flurtamone, Flufenacet, Flupyrsulfuron, Carfentrazon, Mesosulfuron, Iodosulfuron, Pinoxaden, Fenoxaprop, Bifenox, Amidosulfuron, Propoxycarbazone Potatoes: Aclonifen, Prosulfocarb, Metribuzin Maize: Bromoxynil, Terbuthylazin, Mesotrione, Rimsulfuron, Sulcotrione, Nicosulfuron, Bentazon, Dicamba, Metolachlor Rape: Metazachlor, Quinmerac, Dimetachlor, Clomazone, Trifluralin, Picloram, Clopyralid Railway traffic: Atrazin, Desethylatrazin, Desethylsimazin, Bromacil, Desethylterbuthylazin, Simazin, Propazin, Diuron, Dimefuron, Flazasulfuron, Flumioxazin

17 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Example for lists of target pesticides: NRW List (North Rhine-Westphalia) 1,2-Dichlorpropan, 1,3-Dichlorpropen, 1,3-Dichlorpropen, 2,4,5-T, 2,4,5-TP, 2,4-D, 2,4-DB, 2,4-DP, Alachlor, Aldicarb, alpha-Endosulfan, Ametryn, Atrazin, Azinphos-ethyl, Bentazon, beta-Endosulfan, Bromacil, Carbetamid, Chloridazon, Chlortoluron, Clopyralid, Cyanazin, Desethylatrazin, Desethylsimazin, Desethylterbuthylazin, Desmetryn, Diazinon, Dichlobenil, Dichlorbenzamid, Diuron, Lindan, Hexazinon, Isoproturon, Lenacil, Linuron, MCPA, MCPB, MCPP, Metalaxyl, Meta- mitron, Metazachlor, Methabenzthiazuron, Metobromuron, Metolachlor, Metoxuron, Metribuzin, Monolinuron, Monuron, Parathion-ethyl, Parathion-methyl, Pendimethalin, Phenmedipham, Procymidon, Pro- metryn, Propachlor, Propazin, Sebuthylazin, Simazin, Terbuthylazin, Terbutryn, Triadimefon, Triadimenol, Triallat, Trifluralin, Vinclozolin

18 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 TZW lists: A] Lists routinely applied for drinking water analysis List 1 Atrazin Desethylatrazin Propazin Simazin Desisopropylatrazin Terbuthylazin Desethylterbuthylazin Metribuzin Metolachlor Metazachlor Metalaxyl Diclobenil Dichlorbenzamid Pendimethalin Hexazinon Alachlor Trifluralin Propachlor Triallat Atrazin Desethylatrazin Propazin Sebuthylazin Simazin Desisopropylatrazin Terbuthylazin Desethylterbuthylazin Metribuzin Chlortoluron Diuron Isoproturon Linuron Methabenzthiazuron Bromacil Hexazinon List 2 List 3 2,4-D 2,4-DP (Dichlorprop) 2,4,5-T 2,4,5-TP (Fenoprop) MCPA MCPP (Mecoprop) MCPB 2,4-DB Bentazon Triclopyr Fluroxypyr Bromoxynil Ioxynil

19 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 TZW lists: B] Additional lists (applied on request) List 4 List 6 List 7 AMPA Glyphosat Amidosulfuron Bensulfuron-methyl Chlorsulfuron Metsulfuron-methyl Nicosulfuron Primisulfuron-methyl Prosulfuron Thifensulfuron-methyl Triasulfuron Triflusulfuron-methyl List 5 Aldrin alpha-Endosulfan alpha-HCH beta-Endosulfan beta-HCH cis-Chlordan cis-Heptachlorepoxid Cypermethrin Deltamethrin Dieldrin Endosulfansulfat gamma-HCH (Lindan) Heptachlor Hexachlorbenzol (HCB) Isodrin 1,2-Dichlorpropan 1,3-Dichlorpropan 1,3-Dichlorpropen (E-) 1,3-Dichlorpropen (Z-)

20 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Founded in 1992 Objective: Sustainable protection of groundwater and source water used for drinking water production Supporting organisations: municipalities, cities, German waterworks associations, TZW Database contains information e.g. about general water quality parameters, nitrate levels and pesticide concentrations in groundwaters used for drinking water production Database allows for the determination and prediction of trends Example from Baden-Württemberg: Groundwater Database

21 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/ Water utilities Monitoring wells Samples Contribution of water utilities

22 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 GRUNDWASSERDATENBANK Wasserversorgung Target pesticides Group AGroup BGroup C Bentazon Mecoprop Dichlorprop 2,4-D MCPA Dicamba Atrazin Desethylatrazin Desethylterbutylazin Desisopropylatrazin Simazin Terbuthylazin Bromacil Propazin Hexazinon Metolachlor Metazachlor Metalaxyl 2,6-Dichlorbenzamid Diuron Isoproturon Linuron Chlortoluron Methabenzthiazuron

23 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 GRUNDWASSERDATENBANK Wasserversorgung Monitoring campaigns Locations Without positive findings -ABC- With positive findings PPPPP -ABC-

24 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 GRUNDWASSERDATENBANK Wasserversorgung Results for pesticides (2) ParameterSamples> LOQ> 0,1 µg/L Max. Conc. [µg/L] Desethylatrazin ,47 Atrazin ,12 2,6-Dichlorbenzamid ,51 Bentazon ,37 Simazin ,08 Desisopropylatrazin ,14 Diuron ,06 Hexazinon ,06 Bromacil ,12

25 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Pesticide metabolites: Desphenyl-Chloridazon Chloridazon Desphenyl-Chloridazon Metabolite B Chloridazon: Herbicide against weed in beet cultures Methyl-Desphenyl-Chloridazon Metabolite B-1

26 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Desphenyl-Chloridazon in Baden-Württemberg Source waters Drinking waters Desphenyl-Chloridazon in µg/L < 0,0511 0,05 – 0,11 0,1 – 0,59 0,5 – 1,02 1,0 – 5,09 Desphenyl-Chloridazon in µg/L < 0,0518 0,05 – 0,14 0,1 – 0,520 0,5 – 1,04 1,0 – 5,06

27 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Desphenyl-Chloridazon: Consequences Federal Ministry of Baden-Württemberg: Immediate restriction of the use of Chloridazon Producer: Voluntary renunciation for Chloridazon in Europe Decision about classification of Desphenyl-Chloridazon as relevant metabolite is made on a federal level Hessen: Desphenyl-Chloridazon is a relevant metabolite Exceedance of 0.1 µg/L means non-compliance with DWD Permission of the Health authority is required; consumers have to be informed All other federal states: Desphenyl-Chloridazon is not a relevant metabolite

28 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Pesticide metabolites: Dimethylsulfamide (DMS) Tolylfluanide: Fungicide in cultures of fruit, vegetables and plants, and in vineyards Tolylfluanide N,N-Dimethylsulfamide (DMS)

29 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 Dimethylsulfamide: Consequences Authorisation of tolylfluanide was immediately stopped. Products containing tolylfluanide may not be purchased and used anymore in Germany (exception: green houses) Decision about classification of dimethylsulfamide as relevant metabolite is made on a federal level Baden-Württemberg: Dimethylsulfamide is a relevant metabolite Exceedance of 0.1 µg/L means non-compliance with DWD Permission of the Health authority is required; consumers have to be informed All other federal states: Dimethylsulfamide is not a relevant metabolite

30 DVGW-Technologiezentrum Wasser (TZW), Karlsruhe Twinning Project PL06/IB/EN/01 European Drinking Water Directive does not provide any information about which pesticides have to be monitored Information about use of pesticides is scarce and often not available to water suppliers and health authorities In Germany, decision on target list(s) for pesticides is made either by the health authorities, the water utilities, or the laboratories that perform the analyses Different lists on federal or local level exist and most often these lists are based on analytical capabilities No general recommendation for target lists of pesticides can be given Summary


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