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EURL-FV European Union Reference Laboratory Pesticide Residues in Fruits and Vegetables
NUEVA REGLAMENTACION Y GUIAS DE
CONTROL DE CALIDAD EUROPEAS
Amadeo R. Fernández-Alba
Food
Residue Control
Results
Harmonization
World Trade
EU Regulation
Social Perception
Pesticide
Manufacturers
New/Upgrade analytical
Techniques
1.EU REGULATIONS
2.SOCIAL PERCEPTION
3.PESTICIDE MANUFACTURERS
4.WORLD TRADE
5.RESULTS HARMONIZATION
6. NEW/UPGRADE ANAL. TECH.
I. EU PESTICIDE RESIDUE REGULATION
Regulation
Directive
What is a MRL?
Maximum residue level means the upper legal level of a concentration for a pesticide residue in or on food and feed based on
good agricultural practice and the lowest consumer exposure necessary to protect vulnerable consumers.
What is the main principle in setting a MRL? Maximum residue level should be set at the lowest achievable level
consistent with good agricultural practice for each pesticide with a
view to protecting vulnerable groups such as children and the unborn.
The EU approach and legislation on
pesticides – residues
Community Legislation
• Regulation (EC) No 396/2005 and amendments:
– Regulation (EC) No 299/2008 of the European Parliament and of
the Council of 11 March 2008 amending Regulation (EC) No 396/2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin, as regards the implementing powers conferred on the Commission
– Regulation (EC) No 396/2005 of the European Parliament and the Council of 23 February 2005 on maximum residue levels of pesticides in or on food and feed of plant and animal origin and amending Council Directive 91/414/EEC.
Available at: http://ec.europa.eu/sanco_pesticides/public/index.cfm
Reg. (EC) No. 1097/2009 Reg. (EC) No. 304/2010
Reg. (EC) No. 256/2009
Reg. (EC) No. 1050/2009 Reg. (EC) No. 750/2010
Reg. (EC) No. 765/2010
Reg. (EC) No. 893/2010
Reg. (EC) No. 178/2006
Reg. (EC) No. 149/2008
Reg. (EC) No. 839/2008
Reg. (EC) No. 822/2009 Reg. (EC) No. 459/2010
Not yet published
Not yet published
Reg. (EC) No. 260/2008
List of Commodities
Existing EU MRLS
EU temporary MRLs
Pesticides with
no MRL (low risk)
Pesticides with
default limit other than
0.01mg/Kg
Conversion
Factor of MRLs
Fumigants with
special derogations
Comments
Food Law, EFSA and Food Safety
Official Controls on imports
Coordinated Multiannual Community Control Programme, planned within 3 years and including
Baby Food (2006/125/EC and 2006/141/EC) and Organic farming samples to be analysed
Annex I
Annex II
Annexes III A III B
Annex
IV
Annex V
Annex
VI
Annex
VII
Placing PPP in the market
Reg. (EC) No.
299/2008
Harmonised Legislation
Legislation
Reg. (EC) No.178/2002
Reg. (EC) No.16/2011
Reg. (EC) No.882/2004
Reg. (EC) No.669/2009
Reg. (EC) No.1213/2008
Reg. (EC) No.901/2009 Reg. (EC) No.915/2010
Reg. (EC) No.
396/2005
Directive 91/414/EEC Regulation (EC) No. 1107/2009
Regulation (EC) No. 1141/2010
EFSA
FVO DG SANCO
Mechanisms of Control specially through the legislation in place
- Pesticide Legislation: Reg. 299/2008
- Coordinated Programs: Reg. 915/2010
- RASFF: Reg. 16/2011
- MRL Database
- Risk Assessment: Reg.178/2002 & Reg.16/2011
- Data Collection of EU Monitoring: Reg. 82/2004
- Inspections: Reg. 882/2004 & Reg. 669/2009
530 pesticides
Before Reg. No 396/2005
250 pesticides
National
MRLs None, except for feed/fish
0,01 mg/kg
EU-MRLs
850 pesticides
Default
MRLs Only in 2 EU Member
States
Harmonisation of pesticide MRLs
The EU approach and legislation on
pesticides – residue
The EU approach and legislation on pesticides – residue
Which products are covered by legislation?
• 315 commodities – 10 main groups
• 190 existing entries from past Directives
• 125 new entries • Mainly minor crops (e.g. cassava, thyme, lupins),
but also cocoa, coffee, sugar plants, honey
• Fish and plants used in animal feed listed, but for the time being exempted from EU-MRL setting
DATABASE on Active substances
http://ec.europa.eu/sanco_pesticides/public/index.cfm
The EU approach and legislation on pesticides – residue
EU MRLs
AZOXYSTROBIN MRL (mg/kg) IPRODIONE MRL (mg/kg)
Lettuce 3.0 Lettuce 10.0
Grapes 2.0 Cucumber 2.0
Tomatos 2.0 Apples 10.0
Brocoli 0.05 Oranges 0.02
Spinach 0.05 Asparagus 0.02
Tomatoe Pepper Cucumber
Abamectine 0.01 0.01 0.01
Benomyl 0.50 0.10 0.50
Cyromazin 0.50 2.00 0.10
Dimetomorf 0.50 0.02 0.50
Ethiofencarb 2.00 2.00 2.00
Flufenoxuron 0.50 0.50 0.20
Hexaflumuron 0.05 0.50 0.05
Hexitiazox 0.05 0.50 0.10
Imidacloprid 0.10 0.50 0.10
Lufenuron 0.02 0.02 0.02
Methomyl 1.00 1.00 0.02
Oxamyl 2.00 2.00 2.00
Teflubenzuron 0.50 0.50 0.20
Tiabendazole 0.10 1.00 1.00
Acrinathrin 0.10 0.20 0.02
Bifenthrin 0.20 0.20 0.01
Buprofecin 0.50 0.50 0.20
Chlorpyriphos-me 0.50 0.50 0.05
Endosulfan 1.00 1.00 1.00
Malathion 3.00 3.00 3.00
Methalaxyl 0.20 0.50 0.05
Methamidophos 0.50 0.01 1.00
Pyrimiphos-methyl 0.50 1.00 0.20
Procymidone 2.00 2.00 1.00
Maximum Residue Levels (MRLs) authorized in EU (mg/kg)
600
30 40
400
900
30
Pesticide US Codex EU Brazil Korea Taiwan
Bentazone 0.05 0.1 0.1 0.02 0.05 0.5
Clomazone 0.02 --- 0.01 0.1 0.1 ---
Deltamethrin 1 2 2 1 1 0.05
Glyphosate 0.1 30 0.1 0.2 0.1 0.1
Comparison of the different MRLs in rice established by the Codex
Alimentarius, Brazil, US, Taiwan, Korea and the European Union for the most
used herbicides in rice crops and the principal pesticides found in rice
samples.
Pesticide Annex I
91/414
Registered
(General)
In Turkey
Pyrithiobac Not listed Yes
Oxolinic Acid Not listed Yes
Imazapic Not listed Yes
Fluthiacet-Methyl Not listed Yes
Cyclosulfamuron Not listed Yes
Chloroneb Not listed Yes
Brodifacoum Not listed Yes
Anilofos Not listed Yes
Pyrimidifen Not listed Yes
Triosulfuron Not listed Yes
EPN Not listed Yes
Acephate Out Yes
Agrobacterium radiobacter Out Yes
Alachlor Out Yes
Aldicarb Out Yes
Pesticide Annex I
91/414
Registered
(General)
In Turkey
Amitraz Out Yes
Atrazine Out Yes
Imazapic Out Yes
Azinphos-methyl Out Yes
Benfuracarb Out Yes
Benomyl Out Yes
Beta-cypermethrin Out Yes
Brodifacoum Out Yes
Bromacil Out Yes
Bromopropylate Out Yes
Bronopol Out Yes
Cadusafos Out Yes
Carbofuran Out Yes
Carbosulfan Out Yes
Chlorfenapyr Out Yes
MONITORING
2,4-D Carbofuran Dimethoate Fluazifop Lufenuron Phosmet Tebufenpyrad
4,4′-Methoxychlor Carbosulfan Dimethoate Fludioxonil Malathion Phoxim Tecnazene
Abamectin Chlordane Omethoate Flufenoxuron Maneb group Pyraclostrobin Teflubenzuron
Acephate Chlorfenapyr Dimethomorph Fluquinconazole Mepanipyrim Pirimicarb Tefluthrin
Acetamiprid Chlorfenvinphos Dinocap Flusilazole Mepiquat Pirimiphos-methyl Tetraconazole
Acrinathrin Chlormequat Diphenylamine Flutriafol Metalaxyl Prochloraz Tetradifon
Aldicarb Chlorobenzilate Endosulfan Folpet Metconazole Procymidone Thiabendazole
Amitraz Chlorothalonil Endrin Formetanate Methamidophos Profenofos Thiamethoxam
Amitrole Chlorpropham Epoxiconazole Fosthiazate Methidathion Propamocarb Thiacloprid
Azinphos-ethyl Chlorpyriphos Ethephon Glyphosate Methiocarb Propargite Thiophanate-methyl
Azinphos-methyl Chlorpyriphos-methyl Ethion Haloxyfop Methomyl Propiconazole Tolcloflos-methyl
Azoxystrobin Clofentezin Etofenprox HCB Methoxyfenozide Propyzamide Tolylfluanid
Benfuracarb Clothianidin Ethoprophos Heptachlor Monocrotophos Prothioconazole Triadimefon
Bifenthrin Cyfluthrin Fenamiphos Alpha-HCH Myclobutanil Pyrazophos Triadimenol
Bitertanol Cypermethrin Fenarimol Beta-HCH Oxadixyl Pyrethrins Triazophos
Boscalid Cyproconazole Fenazaquin Gamma-HCH Oxamyl Pyridaben Trichlorfon
Bromide ion Cyprodinil Fenbutatin oxide Hexaconazole Oxydemeton-methyl Pyrimethanil Trifloxystrobin
Bromopropylate DDT Fenbuconazole Hexythiazox Paclobutrazole Pyriproxyfen Triflumuron
Bromuconazole Deltamethrin Fenhexamid Imazalil Parathion Quinoxyfen Trifluralin
Bupirimate Diazinon Fenitrothion Imidacloprid Parathion-Methyl Quintozene Triticonazole
Buprofezin Dichlofluanid Fenoxycarb Indoxacarb Pencycuron Resmethrin Vinclozolin
Cadusafos Dichlorvos Fenpropathrin Iprodione Penconazole Spinosad Zoxamide
Camphechlor Dicloran Fenpropimorph Iprovalicarb Pendimethalin Spiroxamine
Captan Dicofol Fenthion Kresoxim-methyl Permethrin Taufluvalinate
Carbaryl Dieldrin Fenvalerate/Esfenvalerate Lambda-cyhalothrin Phenthoate Tebuconazole
Carbendazim Difenoconazole Fipronil Linuron Phosalone Tebufenozide
Pesticide monitored in Coordinated Plan 2010
177 compounds governed by
Regulation (EC) No 396/2005 amending
Directive 91/414/EEC
Overall frequency of samples with and without measurable residues in the
2008 EU coordinated program (≤MRL: Samples with measurable residues
below or at the MRL; >MRL: Samples with residues above the MRL). Total
number of samples: 11610.
Origin of samples (EU: EU, Iceland and Norway; Imported: third countries); surveillance and enforcement samples of fruit,
vegetables, cereals, processed commodities and baby food
Number of residues found in individual surveillance
samples from the national and EU coordinated pesticide monitoring programmes 2008
II. Social Perception and
Consumer Trends
Changes in the Attitude towards Food
P r o d u c t i o n
C o n s u m e r
Year 1945 1950 1960 1970 1980 1990 2000
Increase
Agric.production
Increase
Product Quality
Increase Product Safety
Protect the Environment
Concern Hunger Appetite
Is there anything to
eat? What is there
to eat?
How Safe is Food
How was the Production
In A
nle
hnung
an F
lacho
wsky
2002
Motives for Buying Organic-Food
47
30
29
21
16
15
14
0 10 20 30 40 50
Absence of chemicals and additives
Reminds me of former times
Prevent Illnesses
Better Taste
Safe the planet for future generations
Friendliness to Animals
Support organic farmers
%
Source: Frankfurter Rundschau 07/10/2004
From Michelangelo Annastassiades (CRL Stuttgart)
III. Plant Protection
Industry
Diazinon
Pirimifos-metil
Endosulfan
Chlorothalonil
Chlorpyrifos
Endosulfan sulfato
Vinclozolina
Procimidona
Cipermetrina
Pesticides (1st generation)
Pesticides (new generation)
Methamidophos Methiocarb
Azoxystrobin
Spinosad
Chemical structures for some well-known and new pesticides
Acephate Lindane
Acrinathrin Malathion
Bromopropylate Mecarbam
Chlorothalonil Methamidophos
Chlorpyriphos Methidathion
Chlorpyriphos-methyl Methiocarb
Chlozolinate Omethoate
Dichlofluanid Parathion-methyl
Dichlorvos Procymidone
Dicofol Pyrazophos
Dimethoate Pyridaphenthion
Endosulfan Pyrimiphos-methyl
Fenpropathrin Tetradifon
Fenthion Trichlorfon
Flufenoxuron Quinalphos
Imidacloprid Vinclozoline
Pesticides covered in 1998
Number of target pesticides (in Almería area)
•Decrease of the number of authorized substances
•Absence sometimes of and effective authorized
substances
•Residue appearance of misussed or not authorized
pesticides
IV. Results Harmonization
European Community
27 countries with quite different
size, population, culture, economy….
Harmonization is in progress….
Social perception = Reality?
Labs within Network (EU: N=264)
8+2 10
13 21 35
35 36
40
Belgium
Burgaria
Greece
France
Spain
Germany
Poland
Italy
6 9
Romania
Hungary
5 5
Portugal
UK
4 4
Denmark
Slovenia
2 2
3 3 3
3 4
4
Lithuania
Ireland
Austria
Estonia
Finland
Netherlands
Slovakia
Czech Rep.
2 2
Cyprus
Sweden
1 1
Malta
Latvia
264 1
Average EU
Luxemburg
(1.1) 0.8
0.9 3
1.3
2.4 1.1
1.5
3.6 1.1
2.1 12.2
1.4 0.5
Labs COUNTRY Population
per Lab (mio)
1.7 2.2
2.8 0.4 1.8
5.4 1.4
2.6
0.4 4.5
0.4 2.3
1.9 0.5
Labs COUNTRY Population
per Lab (mio)
No of EU Samples done by MRM
0
1000
2000
3000
4000
5000
EU
PT
-FV
10
-001
EU
PT
-FV
10
-002
EU
PT
-FV
10
-004
EU
PT
-FV
10
-007
EU
PT
-FV
10
-011
EU
PT
-FV
10
-015
EU
PT
-FV
10
-017
EU
PT
-FV
10
-018
EU
PT
-FV
10
-020
EU
PT
-FV
10
-022
EU
PT
-FV
10
-024
EU
PT
-FV
10
-026
EU
PT
-FV
10
-028
EU
PT
-FV
10
-033
EU
PT
-FV
10
-053
EU
PT
-FV
10
-058
EU
PT
-FV
10
-062
EU
PT
-FV
10
-064
EU
PT
-FV
10
-067
EU
PT
-FV
10
-069
EU
PT
-FV
10
-070
EU
PT
-FV
10
-071
EU
PT
-FV
10
-072
EU
PT
-FV
10
-074
EU
PT
-FV
10
-078
EU
PT
-FV
10
-079
EU
PT
-FV
10
-082
EU
PT
-FV
10
-087
EU
PT
-FV
10
-088
EU
PT
-FV
10
-091
EU
PT
-FV
10
-092
EU
PT
-FV
10
-098
EU
PT
-FV
10
-099
EU
PT
-FV
10
-102
EU
PT
-FV
10
-106
EU
PT
-FV
10
-111
EU
PT
-FV
10
-112
EU
PT
-FV
10
-127
EU
PT
-FV
10
-128
EU
PT
-FV
10
-132
EU
PT
-FV
10
-003
EU
PT
-FV
10
-005
EU
PT
-FV
10
-006
EU
PT
-FV
10
-008
EU
PT
-FV
10
-009
EU
PT
-FV
10
-010
EU
PT
-FV
10
-012
EU
PT
-FV
10
-013
EU
PT
-FV
10
-014
EU
PT
-FV
10
-016
EU
PT
-FV
10
-019
EU
PT
-FV
10
-021
EU
PT
-FV
10
-023
EU
PT
-FV
10
-025
EU
PT
-FV
10
-027
EU
PT
-FV
10
-029
EU
PT
-FV
10
-030
EU
PT
-FV
10
-031
EU
PT
-FV
10
-032
EU
PT
-FV
10
-034
EU
PT
-FV
10
-035
EU
PT
-FV
10
-036
EU
PT
-FV
10
-037
EU
PT
-FV
10
-038
EU
PT
-FV
10
-039
EU
PT
-FV
10
-040
EU
PT
-FV
10
-041
EU
PT
-FV
10
-042
EU
PT
-FV
10
-043
EU
PT
-FV
10
-044
EU
PT
-FV
10
-045
EU
PT
-FV
10
-046
EU
PT
-FV
10
-047
EU
PT
-FV
10
-048
EU
PT
-FV
10
-049
EU
PT
-FV
10
-050
EU
PT
-FV
10
-051
EU
PT
-FV
10
-052
EU
PT
-FV
10
-054
EU
PT
-FV
10
-055
EU
PT
-FV
10
-056
EU
PT
-FV
10
-057
EU
PT
-FV
10
-059
EU
PT
-FV
10
-060
EU
PT
-FV
10
-061
EU
PT
-FV
10
-063
EU
PT
-FV
10
-065
EU
PT
-FV
10
-066
EU
PT
-FV
10
-068
EU
PT
-FV
10
-073
EU
PT
-FV
10
-075
EU
PT
-FV
10
-076
EU
PT
-FV
10
-077
EU
PT
-FV
10
-080
EU
PT
-FV
10
-081
EU
PT
-FV
10
-083
EU
PT
-FV
10
-084
EU
PT
-FV
10
-085
EU
PT
-FV
10
-086
EU
PT
-FV
10
-089
EU
PT
-FV
10
-090
EU
PT
-FV
10
-093
EU
PT
-FV
10
-094
EU
PT
-FV
10
-095
EU
PT
-FV
10
-096
EU
PT
-FV
10
-097
EU
PT
-FV
10
-100
EU
PT
-FV
10
-101
EU
PT
-FV
10
-103
EU
PT
-FV
10
-104
EU
PT
-FV
10
-105
EU
PT
-FV
10
-107
EU
PT
-FV
10
-108
EU
PT
-FV
10
-109
EU
PT
-FV
10
-110
EU
PT
-FV
10
-113
EU
PT
-FV
10
-114
EU
PT
-FV
10
-115
EU
PT
-FV
10
-116
EU
PT
-FV
10
-117
EU
PT
-FV
10
-118
EU
PT
-FV
10
-119
EU
PT
-FV
10
-120
EU
PT
-FV
10
-121
EU
PT
-FV
10
-122
EU
PT
-FV
10
-123
EU
PT
-FV
10
-124
EU
PT
-FV
10
-125
EU
PT
-FV
10
-126
EU
PT
-FV
10
-129
EU
PT
-FV
10
-130
EU
PT
-FV
10
-131
No of EU Samples done by MRM
0
1000
2000
3000
4000
5000
EU
PT
-FV
10
-001
EU
PT
-FV
10
-002
EU
PT
-FV
10
-004
EU
PT
-FV
10
-007
EU
PT
-FV
10
-011
EU
PT
-FV
10
-015
EU
PT
-FV
10
-017
EU
PT
-FV
10
-018
EU
PT
-FV
10
-020
EU
PT
-FV
10
-022
EU
PT
-FV
10
-024
EU
PT
-FV
10
-026
EU
PT
-FV
10
-028
EU
PT
-FV
10
-033
EU
PT
-FV
10
-053
EU
PT
-FV
10
-058
EU
PT
-FV
10
-062
EU
PT
-FV
10
-064
EU
PT
-FV
10
-067
EU
PT
-FV
10
-069
EU
PT
-FV
10
-070
EU
PT
-FV
10
-071
EU
PT
-FV
10
-072
EU
PT
-FV
10
-074
EU
PT
-FV
10
-078
EU
PT
-FV
10
-079
EU
PT
-FV
10
-082
EU
PT
-FV
10
-087
EU
PT
-FV
10
-088
EU
PT
-FV
10
-091
EU
PT
-FV
10
-092
EU
PT
-FV
10
-098
EU
PT
-FV
10
-099
EU
PT
-FV
10
-102
EU
PT
-FV
10
-106
EU
PT
-FV
10
-111
EU
PT
-FV
10
-112
EU
PT
-FV
10
-127
EU
PT
-FV
10
-128
EU
PT
-FV
10
-132
EU
PT
-FV
10
-003
EU
PT
-FV
10
-005
EU
PT
-FV
10
-006
EU
PT
-FV
10
-008
EU
PT
-FV
10
-009
EU
PT
-FV
10
-010
EU
PT
-FV
10
-012
EU
PT
-FV
10
-013
EU
PT
-FV
10
-014
EU
PT
-FV
10
-016
EU
PT
-FV
10
-019
EU
PT
-FV
10
-021
EU
PT
-FV
10
-023
EU
PT
-FV
10
-025
EU
PT
-FV
10
-027
EU
PT
-FV
10
-029
EU
PT
-FV
10
-030
EU
PT
-FV
10
-031
EU
PT
-FV
10
-032
EU
PT
-FV
10
-034
EU
PT
-FV
10
-035
EU
PT
-FV
10
-036
EU
PT
-FV
10
-037
EU
PT
-FV
10
-038
EU
PT
-FV
10
-039
EU
PT
-FV
10
-040
EU
PT
-FV
10
-041
EU
PT
-FV
10
-042
EU
PT
-FV
10
-043
EU
PT
-FV
10
-044
EU
PT
-FV
10
-045
EU
PT
-FV
10
-046
EU
PT
-FV
10
-047
EU
PT
-FV
10
-048
EU
PT
-FV
10
-049
EU
PT
-FV
10
-050
EU
PT
-FV
10
-051
EU
PT
-FV
10
-052
EU
PT
-FV
10
-054
EU
PT
-FV
10
-055
EU
PT
-FV
10
-056
EU
PT
-FV
10
-057
EU
PT
-FV
10
-059
EU
PT
-FV
10
-060
EU
PT
-FV
10
-061
EU
PT
-FV
10
-063
EU
PT
-FV
10
-065
EU
PT
-FV
10
-066
EU
PT
-FV
10
-068
EU
PT
-FV
10
-073
EU
PT
-FV
10
-075
EU
PT
-FV
10
-076
EU
PT
-FV
10
-077
EU
PT
-FV
10
-080
EU
PT
-FV
10
-081
EU
PT
-FV
10
-083
EU
PT
-FV
10
-084
EU
PT
-FV
10
-085
EU
PT
-FV
10
-086
EU
PT
-FV
10
-089
EU
PT
-FV
10
-090
EU
PT
-FV
10
-093
EU
PT
-FV
10
-094
EU
PT
-FV
10
-095
EU
PT
-FV
10
-096
EU
PT
-FV
10
-097
EU
PT
-FV
10
-100
EU
PT
-FV
10
-101
EU
PT
-FV
10
-103
EU
PT
-FV
10
-104
EU
PT
-FV
10
-105
EU
PT
-FV
10
-107
EU
PT
-FV
10
-108
EU
PT
-FV
10
-109
EU
PT
-FV
10
-110
EU
PT
-FV
10
-113
EU
PT
-FV
10
-114
EU
PT
-FV
10
-115
EU
PT
-FV
10
-116
EU
PT
-FV
10
-117
EU
PT
-FV
10
-118
EU
PT
-FV
10
-119
EU
PT
-FV
10
-120
EU
PT
-FV
10
-121
EU
PT
-FV
10
-122
EU
PT
-FV
10
-123
EU
PT
-FV
10
-124
EU
PT
-FV
10
-125
EU
PT
-FV
10
-126
EU
PT
-FV
10
-129
EU
PT
-FV
10
-130
EU
PT
-FV
10
-131
NRL No NRL
20000 25000 11000
per year
TOTAL: 151631
1213
CRL
CRL
CRL
CRL
NRL
NRL
NRL
NRL NRL
NRL
NRL
NRL
NRL
NRL
NRL NRL
NRL
NRL
NRL
NRL
NRL
NRL
NRL
NRL
OFL OFL OFL
OFL OFL
OFL
OFL
OFL
OFL
OFL
OFL
OFL
OFL
OFL
OFL
OFL OFL
OFL OFL
OFL
OFL
OFL OFL
OFL
OFL
OFL
OFL
OFL OFL
OFL
OFL
OFL
OFL
OFL
OFL
OFL OFL
OFL
OFL
OFL
OFL
OFL OFL
OFL OFL
OFL OFL
OFL
OFL
EURL
Network
EURL-Central Homepage: www.eurl-pesticides.eu
many laboratories have recently
invested in new higher mass accuracy MS systems that allow them to greatly increase the scope of their
multiresidue methods
Another reason for conducting this screening method proficiency test is to gain information from the
laboratories on the type of software that they use. Whether they are using
commercial software and databases, or whether they are internally constructed and searched manually.
This information will provide an overall view of the purpose of this type of
test, and if, in a near future, there is the need to develop new software.
The EURL-FV aim is to be able to use mass spectrometry based screening
methods routinely, following validation. This is in line with the new Document SANCO/10684/2009
(“Method validation and quality control procedures for pesticide
residues analysis in food and feed”)
General European Commission Proficiency Test Scheme
Data Analysis
Lab 1 Lab 2 Lab 3 Lab 4 Lab 5
CRL-FV
Scientific Group
Reports
Samples and Protocol
INFORMATION
EUPT Web Page Data Analysis
EURL-FV
Scientific Group
Samples and Protocol
INFORMATION
EUPT Web Page
EUPTs performed
Photo description of the test sample
preparation in different EUPT commodities.
A B C D
E F G H
I J K L
A B C D
E F G H
I J K L
12,753 EUPT z-Score Results over
the 10 tests
10 EUPTs z-Score Results
-5,0
-4,0
-3,0
-2,0
-1,0
0,0
1,0
2,0
3,0
4,0
5,0
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300
EUPT1 EUPT2 EUPT3 EUPT4 EUPT5 EUPT6 EUPT7 EUPT8 EUPT9 EUPT10
25%
FFP RSD
50%
25%
50%
65%
of data
86%
of data
3%
of data
4%
of data
3%
of data
4%
of data
z-Scores
10 EUPTs z-Score Results
-5,0
-4,0
-3,0
-2,0
-1,0
0,0
1,0
2,0
3,0
4,0
5,0
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300
EUPT1 EUPT2 EUPT3 EUPT4 EUPT5 EUPT6 EUPT7 EUPT8 EUPT9 EUPT10
10 EUPTs z-Score Results
-5,0
-4,0
-3,0
-2,0
-1,0
0,0
1,0
2,0
3,0
4,0
5,0
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300
EUPT1 EUPT2 EUPT3 EUPT4 EUPT5 EUPT6 EUPT7 EUPT8 EUPT9 EUPT10
25%
FFP RSD
50%
25%
50%
65%
of data
86%
of data
3%
of data
4%
of data
3%
of data
4%
of data
z-Scores
10 EUPTs z-Score Results
-5,0
-4,0
-3,0
-2,0
-1,0
0,0
1,0
2,0
3,0
4,0
5,0
0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300
EUPT1 EUPT2 EUPT3 EUPT4 EUPT5 EUPT6 EUPT7 EUPT8 EUPT9 EUPT10
Qn RSD for 10 European Commission
Proficiency Tests
0
10
20
30
40
50
60
25% FFP - RSD
EUPT - 1 EUPT - 2 EUPT - 3 EUPT - 4 EUPT - 5 EUPT - 6 EUPT - 7 EUPT - 8 EUPT - 9 EUPT - 10
0
10
20
30
40
50
60
25% FFP - RSD
EUPT - 1 EUPT - 2 EUPT - 3 EUPT - 4 EUPT - 5 EUPT - 6 EUPT - 7 EUPT - 8 EUPT - 9 EUPT - 10
V. WORLD TRADE
¿Violative o non Violative?
§§ MRL =
1,0 mg/kg
1,65 mg/kg
Result = 1,65 0,82 mg/kg (k = 2; 95%)
Lab A Lab B
Con expresión de la
incertidumbre (k = 2; 95%)
Lab A Lab B
Sin evaluación de la
incertidumbre
(solo precisión)
Lab A Lab B
0.8
1.2
1.0
1.4
1.6
mg
kg
-1
Valor
mg k
g-1
Expanded uncertainty 50%
Results with Uncertainty (50%)
(k = 2; 95%)
1. 0
1. 8
1. 4
2. 2
2. 4
Results without Uncertainty
MRL = 1.00 mg/kg
Non violative Violative
1.65 mg/kg
2.00 mg/kg
Document N° SANCO/2007/3131
V. NEW ANALYTICAL/INSTRUMENTAL
APPROACHES/CHALLENGES
SOLVENT EXTRACTION METHOD
LC/GC - MS
High Sensitivity (LOQ)
Multiclass compounds
High identification criteria
Centrifugue 5 min. 3700 r.p.m.
Add 15 AcN with 1% of acetic
acid and 200 µL TPP (25 ppm)
Take the supernant to a
vial for analysis
Weigh 15 g of sample
in a 50 ml Falcon tube
Add 6 g MgSO4 anhidrous
+ 2.5 g NaAc·3 H2O and shake vigorously for 4 minutes
Take a 5 ml aliquot from
supernant and add 750 mg MgSO4
anh. + 250 mg PSA
Centrifugue 5 min. 3700 r.p.m.
Centrifugue 5 min. 3700 r.p.m.
Add 10 EtOAc and 200 µL
TPP (25 ppm). Shake 3 sec.
Take the supernant
to a vial for analysis
Weigh 10 g of sample
in a 50 ml Falcon tube
Add 8 g MgSO4 anhidrous
+ 1.5 g NaCl and shake vigorously for 4 minutes
QuEChERS EtOAc method
•20 min ( analysis time) +
10 min (equilibration) = 30 min/analysis
Around 50 analysis/day
EI/PCI - MS/MS
GC-IT-MS (Internal Ionization)
Dic
lorv
os
M
eta
mid
ofo
s/
10 15 20 25 30 35 40 minutos
0
100
200
300
400
500
600
kCounts
Acefa
to
Eto
pro
fos
Dim
eto
ato
Lin
dano
Pro
piz
am
ida
Dia
zin
on
Pir
imeta
nil
Clo
rpirifos
Metil
Vin
clo
zolin
a
Para
tio
n M
etil
Meta
laxil
Pir
imifos M
etil
Metio
carb
C
lorp
irifos
Fen
tio
n
Die
tofe
nca
rb
Tri
ad
imefo
n
Cip
rodin
il P
en
co
nazo
l M
ecarb
am
Quin
alfos
Pro
cim
idona
Tri
adim
enol
Quin
om
etionato
E
nd
osu
lfan I
Hexaco
nazo
l F
en
am
ifo
s B
up
rofe
zin
Mic
lobuta
nil
Bup
irim
ato
En
do
sulfan II
O
xad
ixil
Ofu
race
Tri
azofo
s
Benala
xil En
do
sulfan S
ulfato
Nuari
mo
l D
ico
fol /
Ipro
dio
na
B
rom
opro
pila
to
Bifen
trin
F
en
pro
patrin
T
ebufe
np
irad
Tetr
ad
ifon
Fo
salo
ne
Fen
ari
mol
Pir
azo
fos
Acri
natr
in
Perm
etr
in
Pir
idaben
Cip
erm
etr
inas
Difen
oco
nazo
l D
eltam
etr
in
Spiked pepper extract
(0.50 mg/kg)
PCI
7.00 7.25 7.50 7.75 8.00
0
5
10
15
20
Dic
lorv
os
Me
tam
ido
fos
GC-QqQ-MS/MS
Ion: 126
75 100 125 150 175 200 m/z
0
25
50
75
100
79
94
109
126
141
METAMIDOFOS
min
75 100 125 150 175 200 m/z
0
25
50
75
100
109 127
145
221
DICLORVOS
Ion: 145
Analyst, (2001)
1
2
3
4
5
6
7
8 9
10 11
12 13
14
15
16
17 18
19
20
21
23
24
25
26
1 Dinocap 2 Thiocyclam 3 Thiabendazole, Parathion
4 Methomyl 5 Fenuron
6 Acetamiprid 7 Thiacloprid 8 Imazalil, Aldicarb
9 Monuron 10 Metolcarb
11 Carbofuran 12 Prometryn 13 Diuron, Ethiofencarb
14 Difenoxuron 15 Dimetomorph
16 Methiocarb 17 Terbuthylazine, Spinosyn A 18 Methidation
19 Promecarb 20 Azoxystrobin, Prochloraz, Spinosyn D
21 Diflubenzuron 22 Chlorfenvinphos, Triflumizole 23 Benalaxyl
24 Parathion, Difenoconazole 25 Buprofezin
26 Spiromesifen
22
5 10 15 20 25 30 35 40 45 50 55
Time, min
0,0
1,0e4
2,0e4
3,0e4
4,0e4
5,0e4
6,0e4
7,0e4
8,0e4
9,0e4
1,0e5
1,1e5
1,2e5
1,3e5
Inte
nsity, c
ps
30,00
36,51 5,16
4,80
21,11 5,78
22,69
29,21 16,82 4,12
19,59 39,80 13,12
7,40 35,25
9,94 15,83 26,40
14,62
25,47 9,65 37,03
6,12 49,04
LC-QqQ-MS
CHALLENGES
Matrix Effects In
Pesticide Residue Analysis:
Is The Battle Over?
Problems Technical
Identification
Quantification
LC-QqQ-MS/MS Skimer
After 20 injections
GC-Q-MS Liner after 40 injections
XIC of +MRM (297 pairs): 226.2/170.0 amu from Sample 1 (MRMs 100) of Data MRM pesticides_02.wiff (Turbo Spray) Max. 1.1e6 cps.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 Time, min
0.00
5.00e4
1.00e5
1.50e5
2.00e5
2.50e5
3.00e5
3.50e5
4.00e5
4.50e5
5.00e5
5.50e5
6.00e5
6.50e5
7.00e5
7.50e5
8.00e5
8.50e5
9.00e5
9.50e5
1.00e6
1.05e6
Inte
nsity
, cp
s
11.79
Results
4x10
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
5.5
6
6.5
7
+ TIC MRM 50 ppb std chromatogram 0.1%HCOOH
1 1 2 2 3 3 4 4 5 5
Counts vs. Acquisit ion Time (min)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
4x10
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
5.5
6
6.5
7
+ TIC MRM 50 ppb std chromatogram 0.1%HCOOH
1 1 2 2 3 3 4 4 5 5
Counts vs. Acquisit ion Time (min)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32
0.1% formic
acid 100 ppb
Distribution of retention times take into account the peak width; HPLC application using
0.1% formic acid as modifier
0 0
4
14
56
32
4 4
7
3
1
9
1413
14
22
16
18
33
16
19
21 21
1312
56
3
0 0 00
5
10
15
20
25
30
35
40
45
50
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33
Retention time (min)
Nu
mb
er
of
co
mp
ou
nd
s
I. II. III. IV. V.
23,420,918,114,10 Start time (min) of
time windows
Time windows
Results
Examples for common transitions:
specific
specific
2x10
0
1
2
3
4
+ MRM (223.00000 -> 86.00000) 50 ppb std chromatogram 0.1%HCOOH
2x10
0
1
2
3
4+ MRM (223.00000 -> 148.00000) 50 ppb std chromatogram 0.1%HCOOH
2x10
0
0.5
1
1.5
+ MRM (223.00000 -> 106.00000) 50 ppb std chromatogram 0.1%HCOOH
2x10
0
0.5
1
1.5
+ MRM (223.00000 -> 166.00000) 50 ppb std chromatogram 0.1%HCOOH
Counts vs. Acquisit ion Time (min)
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5 11 11.5 12 12.5 13 13.5 14
223.0/86.0
223.0/148.0
223.0/106.0
223.0/166.0
Aldicarb sulfone=Aldoxycarb
2x10
0
1
2
3
4
+ MRM (223.00000 -> 86.00000) 50 ppb std chromatogram 0.1%HCOOH
2x10
0
1
2
3
4+ MRM (223.00000 -> 148.00000) 50 ppb std chromatogram 0.1%HCOOH
2x10
0
0.5
1
1.5
+ MRM (223.00000 -> 106.00000) 50 ppb std chromatogram 0.1%HCOOH
2x10
0
0.5
1
1.5
+ MRM (223.00000 -> 166.00000) 50 ppb std chromatogram 0.1%HCOOH
Counts vs. Acquisit ion Time (min)
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5 11 11.5 12 12.5 13 13.5 14
223.0/86.0
223.0/148.0
223.0/106.0
223.0/166.0
2x10
0
1
2
3
4
+ MRM (223.00000 -> 86.00000) 50 ppb std chromatogram 0.1%HCOOH
2x10
0
1
2
3
4+ MRM (223.00000 -> 148.00000) 50 ppb std chromatogram 0.1%HCOOH
2x10
0
0.5
1
1.5
+ MRM (223.00000 -> 106.00000) 50 ppb std chromatogram 0.1%HCOOH
2x10
0
0.5
1
1.5
+ MRM (223.00000 -> 166.00000) 50 ppb std chromatogram 0.1%HCOOH
Counts vs. Acquisit ion Time (min)
0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5 11 11.5 12 12.5 13 13.5 14
223.0/86.0
223.0/148.0
223.0/106.0
223.0/166.0
Aldicarb sulfone=Aldoxycarb
butoxycarboxin – aldicarb sulfone
scanned – unscanned transitions are common
Counts vs. Acquisit ion Time (min)
3x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
2.2
2.4
+ MRM (233.00000 -> 72.00000) 50 ppb std chromatogram0.1%HCOOH
2x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%HCOOH
14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5
Counts vs. Acquisit ion Time (min)
3x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
2.2
2.4
+ MRM (233.00000 -> 72.00000) 50 ppb std chromatogram0.1%HCOOH
2x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%HCOOH
14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5
3x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
2.2
2.4
+ MRM (233.00000 -> 72.00000) 50 ppb std chromatogram0.1%HCOOH
2x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%HCOOH
14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5
223.0/72.0
223.0/160.0
Counts vs. Acquisit ion Time (min)
3x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
2.2
2.4
+ MRM (233.00000 -> 72.00000) 50 ppb std chromatogram0.1%HCOOH
2x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%HCOOH
14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5
Counts vs. Acquisit ion Time (min)
3x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
2.2
2.4
+ MRM (233.00000 -> 72.00000) 50 ppb std chromatogram0.1%HCOOH
2x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%HCOOH
14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5
3x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
2.2
2.4
+ MRM (233.00000 -> 72.00000) 50 ppb std chromatogram0.1%HCOOH
2x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
+ MRM (233.00000 -> 160.00000) 50 ppb std chromatogram 0.1%HCOOH
14.5 15 15.5 16 16.5 17 17.5 18 18.5 19 19.5 20 20.5
223.0/72.0
223.0/160.0
fluometuron - diuron
both scanned transitions are common
specific
specific
Without dilution
Tomato
Orange
Leek
Tomato
Orange
Leek
Distribution of mass diferences between ions in database and matrix.
84
38
17
34
83
6
39
9
17
7
76
16
74
38
10
03
60
5
37
6
18
2
91
28
57
62
67
2
38
8
21
0
10
1
45
19
28
79
58
5
31
6
16
8
97
66
27
0
1000
2000
3000
4000
5000
6000
7000
8000
9000
0 - 1 Da 0 - 0.1 Da 0 - 0.04 Da 0 - 0.02 Da 0 - 0.01 Da 0 - 0.005 Da 0 - 0.001 Da
Garlic Coliflower Rice Pepper
R=15000=300/0.02 R=7500=300/0.04
Leek Dil10 Standard 100ppb
Ratio 0.6
Triflumuron? 359.2 > 156.0
Triflumuron? 359.2 > 138.9
Ratio 0.7
Triflumuron 359.2 > 156.0
Triflumuron 359.2 > 138.9
6x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
+ESI Scan (9.994 min) Frag=90.0V EUPT_SC_1PPB_PUERRO.d Subtract
* 361.0288* 360.0336
* 359.0409
359.1971
362.0287
358.3313361.1944359.3360 360.2012
Counts vs. Mass-to-Charge (m/z)
357.8 358 358.2 358.4 358.6 358.8 359 359.2 359.4 359.6 359.8 360 360.2 360.4 360.6 360.8 361 361.2 361.4 361.6 361.8 362 362.2
The fragment and the isotopic profile
of the triflumuron doesn’t appear
TRIFLUMURON in LC-TOF-FULL SCAN
EIC 359,0405
6 x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
+ESI EIC(359.0405) Scan Frag=90.0V EUPT_SC_1PPB_PUERRO.d Smooth
Counts vs. Acquisition Time (min) 8.6 8.8 9 9.2 9.4 9.6 9.8 10 10.2 10.4 10.6 10.8 11 11.2 11.4 11.6 11.8 12 12.2
TRIFLUMURON 11,22 359,0405 [M+H]+ C15H11ClF3N2O3
TRIFLUMURON Cl37 11,22 361,0375 [M+H+2]+ C15H1137ClF3N2O3
TRIFLUMURON F1 11,22 156,0211 C7H7ClNO
TRIFLUMURON F1 Cl37 11,22 158,0181 C7H737ClNO
Problems Quantification
Without Clean-up
With Clean-up
Matrix Matched Calibration
Istopically Labeled Internal Standards
QC PROCEDURES FOR
PEST. RES. ANAL.
Guidelines for Residues
Monitoring Control in the
European Union
Document 7826/VI/97
ISO 17025
Practical design of a batch of samples
STANDARDS
SOLUTIONS
A) 100 Standards x 40 €/Standard = 4000 €
B) 200 Standards x 40 €/Standard = 8000 €
C) 600 Standards x 40 €/Standard = 24000 €
1-2 YEARS
QC Double Check
(every day)
3-6 months
Stability?
How to overcome the problems?
I. Easy and very practical solutions II. Specific strategies III. Most powerful MS technologies
HIGH SENSITIVE LC-MS
QuEChERS
Dilution 2x
No dilution
LC-MS/MS
Dilution 10x
Preparation of the samples
Dilution 5x
Dilution 8x
Dilution 15x
Dilution 50x
Dilution 25x
Dilution 100x
XIC of +MRM (114 pairs): 223.000/56.000 amu Expected RT: 9.6 ID: Acetamiprid2 from Sample 59 (1 ppb zumo mix naranja dil5x) of QuECh... Max. 4.9e4 cps.
8.8 9.0 9.2 9.4 9.6 9.8 10.0 10.2 10.4 10.6 10.8 11.0 11.2 11.4Time, min
0.0
2000.0
4000.0
6000.0
8000.0
1.0e4
1.2e4
1.4e4
1.6e4
1.8e4
2.0e4
2.2e4
2.4e4
2.6e4
2.8e4
3.0e4
3.2e4
3.4e4
3.6e4
3.8e4
4.0e4
4.2e4
4.4e4
4.6e4
4.8e4
Inte
ns
ity
, c
ps
9.70
Acetamiprid
XIC of +MRM (114 pairs): 297.800/255.900 amu Expected RT: 9.9 ID: Imazalil2 from Sample 50 (1 ppb zumo mix pera ) of QuEChERS efecto... Max. 9.8e5 cps.
9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 10.0 10.1 10.2 10.3 10.4 10.5 10.6 10.7Time, min
0.0
5.0e4
1.0e5
1.5e5
2.0e5
2.5e5
3.0e5
3.5e5
4.0e5
4.5e5
5.0e5
5.5e5
6.0e5
6.5e5
7.0e5
7.5e5
8.0e5
8.5e5
9.0e5
9.5e5
9.8e5
Inte
ns
ity
, c
ps
9.83
Imazalil
XIC of +MRM (114 pairs): 222.000/123.100 amu Expected RT: 12.1 ID: Carbofuran2 from Sample 8 (1 ppb puerro dil5x) of .wiff (Turbo Spray... Max. 1.8e5 cps.
11.5 11.6 11.7 11.8 11.9 12.0 12.1 12.2 12.3 12.4 12.5 12.6 12.7 12.8 12.9 13.0Time, min
0.0
1.0e4
2.0e4
3.0e4
4.0e4
5.0e4
6.0e4
7.0e4
8.0e4
9.0e4
1.0e5
1.1e5
1.2e5
1.3e5
1.4e5
1.5e5
1.6e5
1.7e5
1.8e5
Inte
ns
ity
, c
ps
12.30
Carbofuran
Standard 1 μg/l
Matrix Dil.5x
Matrix no dilution
x2
x7
x2
Matrix effect
Acetamiprid
0,0
10,0
20,0
30,0
40,0
50,0
60,0
70,0
0 2 4 6 8
Leek
Orange
Tomato
Matrix effect %
Sig
nal S
upre
ssio
n
No Dil Dil15x Dil10x Dil8x Dil5x Dil2x Dil25x Dil50x
Acetamiprid
0,00E+00
2,00E+06
4,00E+06
6,00E+06
8,00E+06
1,00E+07
1,20E+07
1,40E+07
0 5 10 15 20 25
Solvent
Dil 15x
Dil 5x
No Dil
Matrix effect
Leek
m/z 321.00911 (Matrix)
Thiacloprid (m/z 253.03092)
Leek
No Dil Dil15x Dil10x Dil8x Dil5x Dil2x
% S
ignal S
upre
ssio
n
Dil25x Dil50x Dil100x
Matrix effect
Ethiofencarb
0,0
10,0
20,0
30,0
40,0
50,0
60,0
70,0
80,0
90,0
0 2 4 6 8
Leek
Orange
Tomato
No Dil Dil15x Dil10x Dil8x Dil5x Dil2x Dil25x Dil50x
Ethiofencarb
0,00E+00
1,00E+06
2,00E+06
3,00E+06
4,00E+06
5,00E+06
6,00E+06
7,00E+06
8,00E+06
0 5 10 15 20 25
Solvent
Dil 15x
Dil 5x
Sin dil
Matrix effect
Naranja
Orange
35%
48%
0%
17%No matrix effect
Improves before or with Dil.15x
Improves at high dilutions
(50x-100x)
Doesn´t improve with dilution
Tomato
68%
26%
6%0%
No matrix effect
Improves before or with Dil.15x
Improves at high dilutions
(50x-100x)
Doesn´t improve with dilution
Leek
7%
76%
4%13%
No matrix effect
Improves before or with Dil.15x
Improves at high dilutions
(50x-100x)
Doesn´t improve with dilution
Orange
Tomato
Leek
Orange
35%
48%
0%
17%No matrix effect
Improves before or with Dil.15x
Improves at high dilutions
(50x-100x)
Doesn´t improve with dilution
FULL SCAN High resolution
Mass accuracy
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time, min
2.0e6
6.0e6
1.0e7
1.4e7
1.8e7
2.2e7
2.6e7
3.0e7
3.4e7
3.8e7
4.2e7
Inte
nsity
, cp
s
16.0 18.0 20.0 22.0 24.0 26.0 28.0
Time, min
24.0
(a) XIC [ m/z 404.0 0.5]
16.0 18.0 20.0 22.0 24.0 26.0 28.0
Time, min
24.0
22.5
(b) XIC [ m/z 404.1 0.1]
16.0 18.0 20.0 22.0 24.0 26.0 Time, min
24.0
28.0
(c) XIC [ m/z 404.12 0.02]
13.0 15.0 17.0 19.0 21.0 Time, min
16.3
(a) XIC [ m/z 223.0 0.5]
13.0 15.0 17.0 19.0 21.0 Time, min
16.3
(b) XIC [ m/z 223.0 0.1]
13.0 15.0 17.0 19.0 21.0 Time, min
16.3
(c) XIC [ m/z 223.07 0.01]
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30 Time, min
Inte
nsity
, cp
s
16.0 18.0 20.0 22.0 24.0 26.0 28.0
Time, min
24.0
(a) XIC [ m/z 404.0 0.5]
16.0 18.0 20.0 22.0 24.0 26.0 28.0
Time, min
24.0
22.5
(b) XIC [ m/z 404.1 0.1]
16.0 18.0 20.0 22.0 24.0 26.0 Time, min
24.0
28.0
(c) XIC [ m/z 404.12 0.02]
13.0 15.0 17.0 19.0 21.0 Time, min
16.3
(a) XIC [ m/z 223.0 0.5]
13.0 15.0 17.0 19.0 21.0 Time, min
16.3
(b) XIC [ m/z 223.0 0.1]
13.0 15.0 17.0 19.0 21.0 Time, min
16.3
(c) XIC [ m/z 223.07 0.01]
Azoxystrobin
Thiacloprid
5 ppm
Sulfadimethoxine
1 GHz 4 GHz
C12H15N4O4S+
Exact Mass: 311.0809
H3N N
N
OCH3
OCH3
S
NH2
O O
N
N
OCH3
OCH3
H2N
Exact Mass: 156.0768
S
O O
H2N
Exact Mass: 156.0114
RESOLUTION
DATABASE SEARCH
10
0.15
PESTICIDES in solvent (20-500ppb)
10
0.15
DATABASE SEARCH
PESTICIDES in solvent (20-500ppb)
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30Time, min
1.0e4
3.0e4
5.0e4
7.0e4
9.0e4
1.1e5
1.3e5
1.5e5
1.7e5
1.9e5
Inte
ns
ity, c
ps
16.2
XICXIC
218.0 219.0 220.0 221.0 222.0 223.0 224.0 225.0 226.0 227.0 228.0 229.0m/z, amu
4000.0
8000.0
1.2e4
1.6e4
2.0e4
2.4e4
2.8e4
3.2e4
3.6e4
4.0e4
4.4e4
4.8e4
5.2e4
5.6e4
6.0e4
6.4e4
6.8e4
Inte
ns
ity, c
ou
nts
223.0745
225.0715
m/zm/z 223.0745223.0745
Chlorine isotopic profileChlorine isotopic profile
[M+H]+
FIGURE 1
N
N
Cl
N
CH3CH3
N
CC1010
HH1111
NN44ClClCC
1010HH
1111NN
44ClCl
ACETAMIPRID
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30Time, min
1.0e4
3.0e4
5.0e4
7.0e4
9.0e4
1.1e5
1.3e5
1.5e5
1.7e5
1.9e5
Inte
ns
ity, c
ps
16.2
XICXIC
218.0 219.0 220.0 221.0 222.0 223.0 224.0 225.0 226.0 227.0 228.0 229.0m/z, amu
4000.0
8000.0
1.2e4
1.6e4
2.0e4
2.4e4
2.8e4
3.2e4
3.6e4
4.0e4
4.4e4
4.8e4
5.2e4
5.6e4
6.0e4
6.4e4
6.8e4
Inte
ns
ity, c
ou
nts
223.0745
225.0715
m/zm/z 223.0745223.0745
Chlorine isotopic profileChlorine isotopic profile
[M+H]+
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30Time, min
1.0e4
3.0e4
5.0e4
7.0e4
9.0e4
1.1e5
1.3e5
1.5e5
1.7e5
1.9e5
Inte
ns
ity, c
ps
16.2
XICXIC
218.0 219.0 220.0 221.0 222.0 223.0 224.0 225.0 226.0 227.0 228.0 229.0m/z, amu
4000.0
8000.0
1.2e4
1.6e4
2.0e4
2.4e4
2.8e4
3.2e4
3.6e4
4.0e4
4.4e4
4.8e4
5.2e4
5.6e4
6.0e4
6.4e4
6.8e4
Inte
ns
ity, c
ou
nts
223.0745
225.0715
m/zm/z 223.0745223.0745
Chlorine isotopic profileChlorine isotopic profile
[M+H]+
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30Time, min
1.0e4
3.0e4
5.0e4
7.0e4
9.0e4
1.1e5
1.3e5
1.5e5
1.7e5
1.9e5
Inte
ns
ity, c
ps
16.2
XICXIC
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30Time, min
1.0e4
3.0e4
5.0e4
7.0e4
9.0e4
1.1e5
1.3e5
1.5e5
1.7e5
1.9e5
Inte
ns
ity, c
ps
2 4 6 8 10 12 14 16 18 20 22 24 26 28 30Time, min
1.0e4
3.0e4
5.0e4
7.0e4
9.0e4
1.1e5
1.3e5
1.5e5
1.7e5
1.9e5
Inte
ns
ity, c
ps
16.2
XICXIC
218.0 219.0 220.0 221.0 222.0 223.0 224.0 225.0 226.0 227.0 228.0 229.0m/z, amu
4000.0
8000.0
1.2e4
1.6e4
2.0e4
2.4e4
2.8e4
3.2e4
3.6e4
4.0e4
4.4e4
4.8e4
5.2e4
5.6e4
6.0e4
6.4e4
6.8e4
Inte
ns
ity, c
ou
nts
223.0745
225.0715
m/zm/z 223.0745223.0745
Chlorine isotopic profileChlorine isotopic profile
[M+H]+
FIGURE 1
N
N
Cl
N
CH3CH3
N N
N
Cl
N
CH3CH3
N
CC1010
HH1111
NN44ClClCC
1010HH
1111NN
44ClClCC
1010HH
1111NN
44ClClCC
1010HH
1111NN
44ClCl
ACETAMIPRID
PROBLEMS
sensitivity
quantification
ident. Param.
RETROSPECTIVE ANALYSIS
EASY TO IMPLEMENT
Additional Advantages
Accurate Mass of Diagnostic Frag. Ions Pesticide Family Compound Diagnostic Ion Accurate Mass of
Diagnostic Ion
Phenylureas Diuron Fenuron
Isoproturon Monuron
72.0444
Organophosphates Chlorpyrifos methyl Dimethoate
Malathion
124.9821
Triazines Deethylatrazine Deethylterbuthylazine
Deisopropylatrazine Atrazine
Terbuthylazine
146.0228
146.0228 + 174.0541
Fluorobenzylureas Diflubenzuron Lufenuron Flufenoxuron Teflubenzuron
Hexaflumuron
158.0412
Neonicotinoids Acetamiprid Thiacloprid
126.0105
Conazole Fungicides Bromuconazole Propiconazole
Imazalil
158.9763
S
P
O
O
N O
N
N
N
Cl
NH3H2N N
N
N
Cl
NH3NH
NH3
O
F
F
NCl
Cl
Cl
NON TARGET Searching for UNKNOWN pesticides in food by LC/TOF-MS
(Using the chlorine isotope signature)
8.0 9.0 10.0 11.0 12.0 13.0 14.0 15.0 16.0 17.0 18.0 19.0 20.0 21.0 22.0 23.0 24.0 25.0 26.0 27.0 28.0 29.0 30.0 Time [min]
0.0
2.0e6
4.0e6
6.0e6
8.0e6
1.0e7
1.2e7
1.4e7
1.6e7
1.8e7
2.0e7
2.2e7
2.4e7
2.6e7
2.8e7
3.0e7
3.2e7
3.4e7
3.6e7
3.8e7
4.0e7
4.2e7
4.4e7
4.6e7
4.8e7
5.0e7
5.2e7
5.4e7
5.6e7
5.8e7
6.0e7
Inte
ns
ity, c
ps
26.73
26.09
25.71 28.11
18.01
22.98 28.42 21.66 23.24 25.04
28.85 20.70 24.13
29.06 19.39 20.26
230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 m/z, amu
0.0
5000.0
1.0e4
1.5e4
2.0e4
2.5e4
3.0e4
3.5e4
4.0e4
4.5e4
5.0e4
5.5e4
6.0e4
6.5e4
7.0e4
7.5e4
8.0e4
8.5e4
9.0e4
9.5e4
1.0e5
1.1e5
1.1e5
1.2e5
1.2e5
1.3e5
1.3e5
1.4e5
1.4e5
1.5e5
1.5e5
1.6e5
Inte
nsity
, co
un
ts
311.0716
313.0687
297.0556
299.0529
312.0741
315.0662
298.0588 301.0510
316.0684
Imazalil
14.0160 + CH2
Methyl substituted Imazalil
DBE 7.5
DBE 7.5 Cl
Cl
O
N
N
-CH3
Imazalil methyl-derivate
An impurity from commercial
formulations containing imazalil
Ion Trap MS/MS
m/z 311 269
m/z 297 255
Applications
Code Matrix Origin Screening by LC-TOF-MS Confirmation by LC-QQQ-MS
6
Pomegranate
India
Below TOF LOD Acefate (3ppb)
Carbendazim (155 ppb) Carbendazime (315ppb)
Difenoconazole (14.7 ppb) Difenoconazole (41ppb)
Below TOF LOD Methiocarbsulfoxide (4ppb)
Below TOF LOD Omethoate * (1.8ppb)
7
Pear
Sudáfrica
Below TOF LOD Metoxifenozide (0.2ppb)
Thiacloprid (13 ppb) Thiacloprid (52ppb)
8 Pear Chile Iprodione (214 ppb) Iprodione (415ppb)
10
Lime
Brasil
Imazalil (9 ppb) Imazalil (44ppb)
Prochloraz (242 ppb) Prochloraz (490ppb)
11 White Grape
Argentina Myclobutanil* (8 ppb) Myclobutanil * (8ppb)
12 Red Plum Sudáfrica Iprodione (81.69 ppb) Iprodione (116ppb)
13 White Plum Sudáfrica FREE OF PESTICIDES FREE OF PESTICIDES
14 Kiwi Italia Fenhexamid (2399 ppb) Fenhexamide (5884 ppb)
15 Bean Marruecos FREE OF PESTICIDES FREE OF PESTICIDES
16 Bean Marruecos FREE OF PESTICIDES FREE OF PESTICIDES
17
Pineapple
Costa Rica
Triadimefon * ( 54 ppb) Triadimefon * (74ppb)
Triadimenol * (120 ppb) Triadimenol * (219ppb)
18 Mango Perú Thiabendazole (188 ppb) Thiabendazole (210ppb)
*Out of Annex I **Pending ***Never notified N.A. Not analyzed Applications
4x10
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
Cpd 1: 4.096: +ESI EIC(192.0553, 193.0603, 383.1085) Scan Frag=190.0V garlic_2.d
1 1
3x10
1
2
3
4
5
6
7
8
Cpd 1: 4.096: +ESI ECC Scan Frag=190.0V garlic_2.d
4.096Cpd 1: 4.096
Counts vs. Acquisition Time (min)
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
INTERFERENCE OF CARBENDAZIM IN GARLIC
3x10
0
0.5
1
1.5
2
2.5
3
3.5
4
4.5
5
5.5
Cpd 1: 4.096: +ESI MFE Spectrum (4.000-4.172 min) Frag=190.0V garlic_2.d
192.0553(M+H)+
383.1085(2M+H)+
Response vs. Mass-to-Charge (m/ z)
100 125 150 175 200 225 250 275 300 325 350 375 400 425 450 475 500 525 550 575 600 625 650 675 700 725 750 775 800 825 850 875 900 925 950 975 1000
¿?
5x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
+ESI Scan (3.195 min) Frag=190.0V mix160pest_100ppb_29abr.d Subtract
192.0762
160.0502
Counts vs. Mass-to-Charge (m/ z)
135 140 145 150 155 160 165 170 175 180 185 190 195 200 205 210 215 220 225 230 235 240
[M+H]+ [C10H9O]+
[C9H10N3O3]+
MASS SPECTRUM OF
CARBENDAZIM
Cpd1: 4.096
383.0885
192.0453
160.0502
192.0762
MASS SPECTRUM OF
THE INTERFERENCE [M+H]+
[2M+H]+
Bupirimate
LC/Q/TOF
TOF MODE
7 x10
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
1.2
1.3
1.4
1.5
1.6
+ESI EIC(317.1642) Scan Frag=90.0V Sens1mix160pestFS20ppbPeppers_1.d Noise (PeakToPeak) = 25410.00; SNR (9.166min) = 1851.6
9.166
8.622
8.490 9.314
9.446
Counts vs. Acquisition Time (min)
8.45 8.5 8.55 8.6 8.65 8.7 8.75 8.8 8.85 8.9 8.95 9 9.05 9.1 9.15 9.2 9.25 9.3 9.35 9.4 9.45 9.5 9.55 9.6 9.65 9.7 9.75 9.8 9.85 9.9
6 x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
2.2
+ESI Scan (9.166 min) Frag=90.0V Sens1mix160pestFS20ppbPeppers_1.d
* 317.1659
318.1674
309.1312
319.1629
Counts vs. Mass-to-Charge (m/z)
309 310 311 312 313 314 315 316 317 318 319 320 321 322 323 324 325 326 327 328 329
[M+H]+
Calculated Mass:
317.1642
FULL SCAN SPECTRUM
C13H24N4O3S
Bupirimate
LC/Q/TOF
Q/TOF MODE
5 x10
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
+ESI EIC Product Ion Frag=90.0V (** -> 88.0757, 108.0117, 166.0972, 210.1588) Sens1mix160pestMSMS20ppbPeppers_1.d Smooth Noise (PeakToPeak) = 115.49; SNR (9.176min) = 13910.1
9.176
Counts vs. Acquisition Time (min) 6.5 6.6 6.7 6.8 6.9 7 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9 8 8.1 8.2 8.3 8.4 8.5 8.6 8.7 8.8 8.9 9 9.1 9.2 9.3 9.4 9.5 9.6 9.7 9.8 9.9 10
4 x10
0
0.2
0.4
0.6
0.8
1
1.2
1.4
1.6
1.8
2
2.2
2.4
2.6
2.8
3
3.2
+ESI Product Ion (9.190 min) Frag=90.0V [email protected] (317.1642[z=1] -> **) Sens1mix160pestMSMS20ppbPeppers_1.d
166.0936
317.1591
210.1557 108.0079
237.2030 272.1021
150.0985
194.1253
Counts vs. Mass-to-Charge (m/z) 100 110 120 130 140 150 160 170 180 190 200 210 220 230 240 250 260 270 280 290 300 310 320 330 340 350 360 370 380 390 400 410 420 430 440 450
[M+H]+
Calculated Mass:
317.1642
EIC
MS/MS SPECTRUM (P.I)
C13H24N4O3S
Target analysis
SENSITIVITY
Non target analysis
SENSITIVITY + SEARCHING CAP. & SOFTWARE