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Chemical screening of pesticides through risk identification methods

Chemical screening of pesticides through risk identification methods. Dr. Frank Sacher DVGW-Technologiezentrum Wasser (TZW), Karlsruhe. Outline. Introduction Selection of target pesticides Practical examples from Germany Announcement of the German Health Authority “Saarland lists”

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Chemical screening of pesticides through risk identification methods

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  1. Chemical screening of pesticides through risk identification methods Dr. Frank Sacher DVGW-Technologiezentrum Wasser (TZW), Karlsruhe

  2. Outline • 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

  3. Council Directive 98/83/EC on the quality of water intended for human consumption • ANNEX I, Part B: Chemical parameters

  4. 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. 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 0.030 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. Chemical structures of pesticides

  7. Degradation scheme of atrazine

  8. Standardized analytical methods for pesticides EN ISO 11369 Determination of plant treatment agents using HPLC with UV detection after solid-liquid extraction DIN EN ISO 10695 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 15913 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. 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 * 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. Pesticides in raw waters for drinking water production Based on data from 477 water utilities Source: J. Kiefer & S. Sturm: Final report for research project W 1/02/05

  11. Pesticides in raw waters for drinking water production Source: J. Kiefer & S. Sturm: Final report for research project W 1/02/05

  12. Pesticides in raw waters for drinking water production Source: J. Kiefer & S. Sturm: Final report for research project W 1/02/05

  13. Selection of target pesticides Limited information on pesticide use in catchment area Large variety of pesticides that might occur in source waters • Analytical limitations • Limitations of costs

  14. Practical strategies in Germany • 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

  15. Example for lists of target pesticides:BGA List (1986) 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 Table 1: 1. Aldicarb 12. Isoproturon 2. Atrazin 13. MCPA 3. Bentazon 14. Mecoprop 4. Bromacil 15. Metazachlor 5. Chloridazon 16. Methabenzthiazuron 6. Chlortoluron 17. Metobromuron 7. Clopyralid 18. Metolachlor 8. 1,2-Dichlorpropan 19. Metoxuron 9. 1,3-Dichlorpropen 20. Propazin 10. Diuron 21. Simazin 11. Endosulfan 22. Terbuthylazin

  16. 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. 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. TZW lists:A] Lists routinely applied for drinking water analysis List 1 List 2 List 3

  19. TZW lists:B] Additional lists (applied on request) List 4 List 6 List 7 List 5

  20. Example from Baden-Württemberg:Groundwater Database • 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

  21. Contribution of water utilities

  22. GRUNDWASSERDATENBANK Wasserversorgung Target pesticides

  23. GRUNDWASSERDATENBANK Wasserversorgung Monitoring campaigns

  24. GRUNDWASSERDATENBANK Wasserversorgung Results for pesticides (2)

  25. Desphenyl-Chloridazon Metabolite B Chloridazon Methyl-Desphenyl-Chloridazon Metabolite B-1 Pesticide metabolites: Desphenyl-Chloridazon • Chloridazon: Herbicide against weed in beet cultures

  26. Desphenyl-Chloridazon in Baden-Württemberg Source waters Drinking waters

  27. 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. N,N-Dimethylsulfamide (DMS) Tolylfluanide Pesticide metabolites: Dimethylsulfamide (DMS) • Tolylfluanide: Fungicide in cultures of fruit, vegetables and plants, and in vineyards

  29. 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. Summary • 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

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