risk assessment of chemical mixtures - europa. greenpeace.pdfpesticides risk assessment 3 •1300...
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GREENPEACE RESEARCH LABORATORIESInnovation Centre Phase 2
University of ExeterRennes Drive, EX4 4RN
Exeter
@GPScienceUnit
EFSA 2019 Roundtable with NGOs:
Risk Assessment of Chemical MixturesBrussels, 13 February 2019
+44 (0) 1392 247920
GREENPEACE SCIENCE UNIT
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• Analytical chemistry and toxicology• Terrestrial and marine ecology• Climate sciences
PESTICIDES RISK ASSESSMENT
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• 1300 pesticides in EU database1
• 490 pesticides approved in the EU2
• Individual pesticide risk quotient:
RQi = concentrationi / EQSi
• UBA: EQS for 157 pesticides3
• Different sources for EQSs, different figures
• Which EQSs should be used?
1 Council European Union Regulation 1107/2009, L309/1, O. J. Eur. Union (24.11.09), n.d.2 Pesticides database of the European Commission, 2018. http://ec.europa.eu/food/ plant/pesticides/eu-pesticides-
database/public/?Event=activesubstance.selection & language=EN3 Regulatory acceptable concentration for selected crop protection agents. Federal Environment Agency of Germany [WWW Document],
n.d. URL https://webetox.uba.de/webETOX/public/basics/literatur.do?id=24559
Pesticides with EQS by UBA
Pesticides in EU database
MIXTURES OF SUBSTANCES
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• Is it possible to have a real sample containing only one bioactive substance?
– Pesticides
– Antimicrobials
– Steroids
– …
• Is it possible to quantify all the bioactive agents present in a sample?
• Is it feasible to consider all the possible interactions between all the bioactive compounds in the sample?
– Potentiation
– Synergism
– Antagonism
– …
MIXTURES OF SUBSTANCES
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The concentration addition approach is used by default:
RQsample = Σ Rqi
– Not all the bioactive agents are monitored
– Not even all the pesticides are monitored
– Different EQSs for the same compound in the literature
– EQSs are not available for all the substances
– Effects of all the different compounds cannot have the same weight
SUMMER 2018 SCREENING
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• Samples:
– 29 snap samples
– Small streams
– 10 countries in the EU
• Screening for:
– Pesticides
– Veterinary drugs
SUMMER 2018 SCREENING
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Compounds found across samples:
– 103 different pesticides
– 21 different veterinary drugs
SPE-LC-HRMS/MS
Q Exactive Focus LC-MS
• Detection of:
– 275 pesticides
– 101 veterinary drugs
• Quantification of:
– 254 pesticides
– LOQs < 5 ng L-1
SUMMER 2018 SCREENING
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0 10 20 30 40 50 60 70 80
NL1
DK3
DK2
NL2
FR1
FR2
PL2
IT3
DK1
SP1
UK1
AT3
PL3
IT1
IT2
DE2
UK2
FR3
SP2
AT1
DE3
SP3
BG1
DE1
PL1
BG3
AT2
NL3
BG2
Number of pesticides
Sam
ple
Mixtures of pesticides
70 pesticides in samples BG2
All the samples carried a mixture of pesticides and, in most cases, other bioactive substances:
SUMMER 2018 SCREENING
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0 1 2 3 4 5 6
DK2
DK3
PL3
PL2
FR2
NL1
IT3
AT3
DE2
UK1
DK1
DE3
UK2
NL2
SP2
SP1
BG3
SP3
BG1
NL3
DE1
PL1
FR1
FR3
IT1
IT2
AT1
AT2
BG2
log [concentration ng L-1]
Sam
ple
Summed concentration of pesticides
94.02 µg L-1
3.24 µg L-1
1.56 µg L-1
Very high summed concentrations of pesticides in some samples:
ppbppt
SUMMER 2018 SCREENING
100 10 20 30 40 50 60 70 80 90 100
ChlortoluronClomazone
TerbumetonMCPA
ProsulfocarbChloridazon
FlufenacetPiperonyl-butoxide
ThiamethoxamThiacloprid
GriseofulvinIsoproturon
AtrazineEpoxiconazole
PrometrynPropiconazoleThiabendazole
BentazoneBoscalid
DiuronNicosulfuron
TerbutrynDimethenamid
AzoxystrobinFluopyram
ImidaclopridMetolachlor
CarbendazimTebuconazole
Terbuthylazine
%
Pes
tici
de
Detection frequency (top 30)
Herbicides detected more frequently than fungicides and insecticides:
SUMMER 2018 SCREENING
110 1 2 3 4 5
Diuron
Clomazone
Lenacil
Isoproturon
Chloridazon
Metconazole
Florasulam
Thiabendazole
Triadimefon
Boscalid
Carbendazim
Nicosulfuron
Fluopyram
Metobromuron
Epoxiconazole
Propiconazole
Piperonyl-butoxide
Tebuconazole
Bentazone
Metamitron
Propyzamide
Flufenacet
Metolachlor
Dimethoate
Terbuthylazine
Prosulfocarb
Ethofumesate
2,4-D
MCPA
Dimethenamid
log [concentration ng L-1]
Pes
tici
de
Maximum concentration (top 30)
ppbppt
59.85 µg L-1
10.01 µg L-1
9.70 µg L-1
Some very high maximum concentrations:
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• 103 pesticides detected in the samples
– Only 58 of these pesticides had an EQS for acute toxicity by the UBA
• 24 pesticides detected are banned in the EU
– Only 2 of these banned pesticides had an EQS
SUMMER 2018 SCREENING
2,4-D Thiacloprid Chlorpyrifos-ethyl
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SUMMER 2018 SCREENING
0 1 2 3 4 5 6 7 8 9 10
Nicosulfuron in AT2
Imidacloprid in DK1
Clothianidin in DE1
Imidacloprid in DE1
Imidacloprid in SP3
Chlorpyrifos-ethyl in BG2
Thiacloprid in BG3
2,4-D in BG2
RQ
Pes
ticd
e in
sam
ple
Top 8 exceedances
15 individual pesticides exceeded the EQS:
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SUMMER 2018 SCREENING
0% 2% 4% 6% 8% 10% 12% 14% 16% 18% 20%
Thiacloprid
Terbuthylazine
Nicosulfuron
MCPA
Chlorpyrifos-Ethyl
Carbendazim
2,4-D
Clothianidin
Imidacloprid
%
Pes
ticd
e
Exceedance frequency
Neonicotinoid insecticides exceeded the EQSs more frequently:
Imidacloprid
Clothianidin
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SUMMER 2018 SCREENING
0 5 10 15 20 25
FR2DK3
DK2NL1SP1
AT3NL2IT3
NL3DE2BG1
PL3PL2FR1
UK5IT1
DE3
SP2PL1IT2
UK4
FR3DK1AT1
AT2BG3SP3
DE1BG2
RQsample
Sam
ple
Risk Quotient by sample
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13 samples with total RQ >1:
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Limitations of this risk assessment:
• Only 254 pesticides were quantified
• No other bio-active compounds were taken into account at quantitative level
• Only 56% of pesticides detected have an EQS
• Only 8% of legacy pesticides detected have an EQS
SUMMER 2018 SCREENING
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THANKS!GREENPEACE RESEARCH LABORATORIES
Innovation Centre Phase 2University of Exeter
Rennes Drive, EX4 4RN Exeter
@GPScienceUnit
+44 (0) 1392 247920