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