Transcript Twinning project Pesticides a.o.

Twinning Project PL06/IB/EN/01
Chemical screening of
pesticides through risk
identification methods
Dr. Frank Sacher
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
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
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
Unit
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
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.
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 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 pesticides
Cl
N
CH3 CH2 NH
Cl
Cl
N
N
NH CH
N
CH3 CH2 NH
NH
O
C
NH CH2 CH3
N
N
CH3
CH3
CH3
Cl
N
N
CH3
CH3
N
CH3
CH3 C NH
CH3
CH
NH
N
O
C
CH3
N
NH CH2 CH3
CH3
CH3
Cl
Cl
Cl
O CH2 COOH
Cl
H
H
Cl
Cl
H
H
Cl
H
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
H
Cl
Cl
C2H5
S
O P O
O
C2H5
NO2
Twinning Project PL06/IB/EN/01
Degradation scheme of atrazine
Cl
N
N
CH3
CH3
CH
NH
Cl
N
NH CH2 CH3
N
Cl
N
N
OH
N
N
CH3
CH3
N
CH3
CH
NH
NH2
N
NH2
NH CH2 CH3
N
CH
NH
N
NH CH2 CH3
CH3
OH
OH
Cl
N
N
N
CH
NH2
N
N
N
N
CH3
NH2
NH
N
CH3
OH
N
NH2
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
N
N
NH2
NH2
NH2
N
NH CH2 CH3
Twinning Project PL06/IB/EN/01
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 automatedmultiple-development technique (AMD)
DIN 38407, part 22 (F22) Determination of glyphosate and AMPA by HPLC, postcolumn 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
intended for human consumption
 ANNEX III, Part 2: Parameters for which performance
characteristics are specified
Parameter
Trueness*
Precision*
LOD*
Pesticides
25
25
25
Conditions
Notes
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 production
295 (62%)
182 (38%)
no findings (< LOQ)
positive findings (> LOQ)
Based on data from 477 water utilities
Source: J. Kiefer & S. Sturm: Final report for research project W 1/02/05
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Pesticides in raw waters for drinking water production
160
140
Number
120
100
80
60
40
20
Di
ur
on
Si
m
az
Is
2,
in
o
6p
D
ro
ic
tu
hl
ro
or
n
be
nz
am
id
Be
M
ec
nt
az
op
on
ro
p
(M
CP
P)
De
Br
si
so
om
pr
ac
op
il
yl
at
ra
Te
zi
n
rb
ut
yl
az
in
He
xa
zi
no
n
Pr
op
az
De
in
se
M
th
CP
yl
te
A
rb
ut
yl
az
Ch
in
lo
rto
lu
ro
M
et
n
az
ac
hl
or
az
in
At
r
De
se
th
yl
at
r
az
in
0
Source: J. Kiefer & S. Sturm: Final report for research project W 1/02/05
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Pesticides in raw waters for drinking water production
50
43
7
metabolites
not authorised
authorised
Source: J. Kiefer & S. Sturm: Final report for research project W 1/02/05
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Example for lists of target pesticides:
BGA List (1986)
Table 1:
1. Aldicarb
2. Atrazin
3. Bentazon
4. Bromacil
5. Chloridazon
6. Chlortoluron
7. Clopyralid
8. 1,2-Dichlorpropan
9. 1,3-Dichlorpropen
10. Diuron
11. Endosulfan
12. Isoproturon
13. MCPA
14. Mecoprop
15. Metazachlor
16. Methabenzthiazuron
17. Metobromuron
18. Metolachlor
19. Metoxuron
20. Propazin
21. Simazin
22. Terbuthylazin
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
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
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
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, Metamitron, Metazachlor, Methabenzthiazuron, Metobromuron, Metolachlor,
Metoxuron, Metribuzin, Monolinuron, Monuron, Parathion-ethyl,
Parathion-methyl, Pendimethalin, Phenmedipham, Procymidon, Prometryn, Propachlor, Propazin, Sebuthylazin, Simazin, Terbuthylazin,
Terbutryn, Triadimefon, Triadimenol, Triallat, Trifluralin, Vinclozolin
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
TZW lists:
A] Lists routinely applied for drinking water analysis
Atrazin
Atrazin
List 1
Desethylatrazin
List 2
Desethylatrazin
2,4-D
List 3
2,4-DP (Dichlorprop)
Propazin
Propazin
2,4,5-T
Simazin
Sebuthylazin
2,4,5-TP (Fenoprop)
Desisopropylatrazin
Simazin
MCPA
Terbuthylazin
Desisopropylatrazin
MCPP (Mecoprop)
Desethylterbuthylazin
Terbuthylazin
MCPB
Metribuzin
Desethylterbuthylazin
2,4-DB
Metolachlor
Metribuzin
Bentazon
Metazachlor
Chlortoluron
Triclopyr
Metalaxyl
Diuron
Fluroxypyr
Diclobenil
Isoproturon
Bromoxynil
Dichlorbenzamid
Linuron
Ioxynil
Pendimethalin
Methabenzthiazuron
Hexazinon
Bromacil
Alachlor
Hexazinon
Trifluralin
Propachlor
Triallat
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
TZW lists:
B] Additional lists (applied on request)
List 4
AMPA
Glyphosat
List 6
Aldrin
alpha-Endosulfan
1,3-Dichlorpropan
1,3-Dichlorpropen (E-)
beta-Endosulfan
1,3-Dichlorpropen (Z-)
Amidosulfuron
cis-Chlordan
Bensulfuron-methyl
cis-Heptachlorepoxid
Chlorsulfuron
Cypermethrin
Metsulfuron-methyl
Deltamethrin
Nicosulfuron
Dieldrin
Primisulfuron-methyl
Endosulfansulfat
Prosulfuron
gamma-HCH (Lindan)
Thifensulfuron-methyl
Heptachlor
Triasulfuron
Hexachlorbenzol (HCB)
Triflusulfuron-methyl
Isodrin
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
1,2-Dichlorpropan
alpha-HCH
beta-HCH
List 5
List 7
Twinning Project PL06/IB/EN/01
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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Contribution of water utilities
2006
2007
Water utilities
672
663
Monitoring wells
2223
2244
Samples
4804
4895
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
GRUNDWASSERDATENBANK
Target pesticides
Wasserversorgung
Group A
Bentazon
Mecoprop
Dichlorprop
2,4-D
MCPA
Dicamba
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Group B
Atrazin
Desethylatrazin
Desethylterbutylazin
Desisopropylatrazin
Simazin
Terbuthylazin
Bromacil
Propazin
Hexazinon
Metolachlor
Metazachlor
Metalaxyl
2,6-Dichlorbenzamid
Group C
Diuron
Isoproturon
Linuron
Chlortoluron
Methabenzthiazuron
Twinning Project PL06/IB/EN/01
GRUNDWASSERDATENBANK
Monitoring campaigns
Wasserversorgung
Locations
Without positive
findings
With positive
findings
2008
2009
2010
2010
2011
-
A
B
C
-
P
P
P
P
P
-
A
B
C
-
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
GRUNDWASSERDATENBANK
Results for pesticides (2)
Wasserversorgung
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
1
0,14
Diuron
2.164
8
0
0,06
Hexazinon
2.277
7
0
0,06
Bromacil
2.269
7
1
0,12
Parameter
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
Pesticide metabolites: Desphenyl-Chloridazon
 Chloridazon: Herbicide against weed in beet cultures
O
Cl
H N
NH2
N
O
Desphenyl-Chloridazon
Metabolite B
Cl
N
NH2
N
Chloridazon
O
Cl
H3C N
NH2
N
Methyl-Desphenyl-Chloridazon
Metabolite B-1
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
< 0,05
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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
< 0,05
18
0,05 – 0,1
4
0,1 – 0,5
20
0,5 – 1,0
4
1,0 – 5,0
6
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
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
H3C
S CCl2F
N
CH3
SO2 N
CH3
Tolylfluanide
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
H2N SO2 N
CH3
CH3
N,N-Dimethylsulfamide
(DMS)
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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe
Twinning Project PL06/IB/EN/01
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
DVGW-Technologiezentrum Wasser (TZW), Karlsruhe