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
Parameter
Parametric value
Unit
Notes
Pesticides
0.10
µg/l
Notes 6 and 7
Pesticides - Total
0.50
Notes 6 and 8

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. No information included about which pesticides have to be monitored!!!
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. Chemical structures of pesticides

7. Degradation scheme of atrazine

8. 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. 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
Parameter
Trueness*
Precision*
LOD*
Conditions
Notes
Pesticides 25
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. 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
Large variety of pesticides that might occur in source waters
Limited information on pesticide use in catchment area
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 Mecoprop
4. Bromacil 15. Metazachlor
5. Chloridazon Methabenzthiazuron
6. Chlortoluron Metobromuron
7. Clopyralid Metolachlor
8. 1,2-Dichlorpropan 19. Metoxuron
9. 1,3-Dichlorpropen 20. Propazin
10. Diuron 21. Simazin
11. Endosulfan 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
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
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
List 1
List 2
List 3

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

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
2006
2007
Water utilities
672
663
Monitoring wells
2223
2244
Samples
4804
4895

22. GRUNDWASSERDATENBANK Wasserversorgung
Target pesticides
Group A
Group B
Group 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. GRUNDWASSERDATENBANK Wasserversorgung
Monitoring campaigns
Locations 
2008
2009
2010
2011
Without positive findings - A B C
With positive findings P

24. Results for pesticides (2)
GRUNDWASSERDATENBANK
Wasserversorgung
Results for pesticides (2)
Parameter
Samples
> LOQ
> 0,1 µg/L
Max. Conc. [µg/L]
Desethylatrazin
2.349
358 23
0,47
Atrazin
2.348
138  1
0,12
2,6-Dichlorbenzamid
2.276
102 16
0,51
Bentazon
2.131
  33  7
0,37
Simazin
2.341
  24  0
0,08
Desisopropylatrazin
2.337
  14
0,14
Diuron
2.164
   8
0,06
Hexazinon
2.277
   7
Bromacil
2.269 1

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

26. Desphenyl-Chloridazon in Baden-Württemberg
Source waters
Desphenyl-Chloridazon in µg/L
< 0,05 11
0,05 – 0,1 1
0,1 – 0,5 9
0,5 – 1,0 2
1,0 – 5,0
Drinking waters
Desphenyl-Chloridazon in µg/L
< 0,05 18
0,05 – 0,1 4
0,1 – 0,5 20
0,5 – 1,0
1,0 – 5,0 6

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

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