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DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Chemical screening of Chemical screening of
pesticides through risk pesticides through risk
identification methodsidentification methods
Dr. Frank Sacher
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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
OutlineOutline
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Council Directive 98/83/EC on the quality of water Council Directive 98/83/EC on the quality of water intended for human consumptionintended for human consumption
ANNEX I, Part B: Chemical parameters
ParameterParametric
valueUnit Notes
Pesticides 0.10 µg/l Notes 6 and 7
Pesticides - Total 0.50 µg/l Notes 6 and 8
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Council Directive 98/83/EC on the quality of water Council Directive 98/83/EC on the quality of water intended for human consumptionintended 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.
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Council Directive 98/83/EC on the quality of water Council Directive 98/83/EC on the quality of water intended for human consumptionintended 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!!!
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Chemical structures of pesticidesChemical structures of pesticides
N
N
N
NHNHCH2CH3 CHCH3
CH3
Cl
N
N
N
NHNHCH2CH3
Cl
CH2 CH3
N
N
N
NHNH
Cl
CH2 CH3CCH3
CH3
CH3
C
O
NCH3
CH3NH
Cl
ClC
O
NCH3
CH3NHCH
CH3
CH3
O CH2 COOH
Cl
Cl Cl
Cl
Cl
ClCl
HH
H
H
Cl
H
H
P
S
OO
OC2H5
C2H5
NO2
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Degradation scheme of atrazineDegradation scheme of atrazine
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Standardized analytical methods for pesticidesStandardized 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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Council Directive 98/83/EC on the quality of water Council Directive 98/83/EC on the quality of water intended for human consumptionintended for human consumption
ANNEX III, Part 2: Parameters for which performance characteristics are specified
Parameter Trueness* Precision* LOD* Conditions Notes
Pesticides 25 25 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.
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Pesticides in raw waters for drinking water productionPesticides 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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
0
20
40
60
80
100
120
140
160
Deseth
ylat
razin
Atrazin
Diuro
n
Simazin
Isopro
turo
n
2,6-D
ichlo
rbenza
mid
Bentazo
n
Meco
prop (M
CPP)
Brom
acil
Desiso
propyla
trazin
Terbuty
lazin
Hexazin
on
Propaz
in
MCPA
Deseth
ylte
rbuty
lazin
Chlorto
luro
n
Meta
zach
lor
Nu
mb
er
Source: J. Kiefer & S. Sturm: Final report for research project W 1/02/05
Pesticides in raw waters for drinking water productionPesticides in raw waters for drinking water production
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 productionPesticides in raw waters for drinking water production
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Selection of target pesticidesSelection 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
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 GermanyPractical strategies in Germany
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Example for lists of target pesticides:Example for lists of target pesticides:BGA List (1986)BGA List (1986)
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
Table 2 (optional):23. Alachlor24. Amitrol25. Azinphos-ethyl26. Carbofuran27. Chlorfenvinphos28. 2,4-D29. Dicamba30. Dichlobenil31. Dichlorprop32. Hexazinon33. Lindan34. Monuron35. Parathion36. Pyridat
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Example for lists of target pesticides:Example for lists of target pesticides:“Saarland lists”“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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Example for lists of target pesticides:Example for lists of target pesticides:“NRW List” (North Rhine-Westphalia)“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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
TZW lists:TZW lists:A] Lists routinely applied for drinking water analysisA] 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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
TZW lists:TZW lists:B] Additional lists (applied on request)B] Additional lists (applied on request)
List 4 List 6 List 7AMPA
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-)
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:Example from Baden-Württemberg:Groundwater DatabaseGroundwater Database
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
2006 2007
Water utilities 672 663
Monitoring wells 2223 2244
Samples 4804 4895
Contribution of water utilitiesContribution of water utilities
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
GRUNDWASSERDATENBANK WasserversorgungTarget pesticidesTarget pesticides
Group A Group B Group C
BentazonMecopropDichlorprop2,4-DMCPADicamba
AtrazinDesethylatrazinDesethylterbutylazinDesisopropylatrazinSimazinTerbuthylazinBromacilPropazinHexazinonMetolachlorMetazachlorMetalaxyl2,6-Dichlorbenzamid
DiuronIsoproturonLinuronChlortoluronMethabenzthiazuron
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
GRUNDWASSERDATENBANK WasserversorgungMonitoring campaignsMonitoring campaigns
Locations 2008 2009 2010 2010 2011
Without positive findings
- A B C -
With positive findings
P P P P P
- A B C -
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
GRUNDWASSERDATENBANK WasserversorgungResults for pesticides (2)Results for pesticides (2)
Parameter Samples > LOQ > 0,1 µg/LMax. 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 1 0,14
Diuron 2.164 8 0 0,06
Hexazinon 2.277 7 0 0,06
Bromacil 2.269 7 1 0,12
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Pesticide metabolites: Desphenyl-ChloridazonPesticide metabolites: Desphenyl-Chloridazon
N
N
NH2
ClO
Chloridazon
Desphenyl-ChloridazonMetabolite B
N
N
NH2
ClO
H
Chloridazon: Herbicide against weed in beet cultures
Methyl-Desphenyl-ChloridazonMetabolite B-1
N
N
NH2
ClO
H3C
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Desphenyl-Chloridazon in Baden-WürttembergDesphenyl-Chloridazon in Baden-Württemberg
Source waters
Drinking 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 9
Desphenyl-Chloridazon in µg/L
< 0,05 18
0,05 – 0,1 4
0,1 – 0,5 20
0,5 – 1,0 4
1,0 – 5,0 6
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Desphenyl-Chloridazon: ConsequencesDesphenyl-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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Pesticide metabolites: Dimethylsulfamide (DMS)Pesticide metabolites: Dimethylsulfamide (DMS)
Tolylfluanide: Fungicide in cultures of fruit, vegetables and plants, and in vineyards
Tolylfluanide
H3C NS
SO2
CCl2F
NCH3
CH3
N,N-Dimethylsulfamide(DMS)
SO2 NCH3
CH3H2N
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Dimethylsulfamide: ConsequencesDimethylsulfamide: 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
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
SummarySummary