dvgw-technologiezentrum wasser (tzw), karlsruhe twinning project pl06/ib/en/01 chemical screening of...

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




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



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




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.




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!!!



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



Degradation scheme of atrazineDegradation scheme of atrazine



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




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.



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



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





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



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



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



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



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



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



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-)



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



2006 2007

Water utilities 672 663

Monitoring wells 2223 2244

Samples 4804 4895

Contribution of water utilitiesContribution of water utilities



GRUNDWASSERDATENBANK WasserversorgungTarget pesticidesTarget pesticides

Group A Group B Group C

BentazonMecopropDichlorprop2,4-DMCPADicamba

AtrazinDesethylatrazinDesethylterbutylazinDesisopropylatrazinSimazinTerbuthylazinBromacilPropazinHexazinonMetolachlorMetazachlorMetalaxyl2,6-Dichlorbenzamid

DiuronIsoproturonLinuronChlortoluronMethabenzthiazuron



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 -



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



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



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



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



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



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



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

dvgw-technologiezentrum wasser (tzw), karlsruhe twinning project pl06/ib/en/01 chemical screening of...

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