Almería 23 rd -25 th October th Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides

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2 ORGANISING GROUP Almería 23 rd -25 th October 2013 DG SANCO Dr. Amadeo R. Fernández-Alba Dr. Milagros Mezcua Mr. Octavio Malato Mrs. Carmen Ferrer STATISTICAL GROUP Dr. Carmelo Rodríguez QUALITY CONTROL GROUP Dr. Antonio Valverde Mr. Stewart Reynolds EUPT-Panel Mrs. Almut Bitterhof Mrs. Veerle Vanheusden ADVISORY GROUP Dr. Michelangelo Anastassiades Mr. Richard Fussell Dr. Miguel Gamón Dr. Magnus Jezussek Dr. André de Kok Mr. Ralf Lippold Dr. Sonja Masselter Dr. Tuija Pihlström Dr. Mette Erecius Poulsen Dr. Darinka Stajnbaher

3 Participation Participation No. Of Labs

4 Country No. of Labs Country No. of Labs Country No. of Labs Austria 3 (-1) Greece 10 Portugal 3 Belgium 8 (+4) Hungary 4 Romania 3 Brazil 1 (-1) Iceland 1 Saudi Arabia 1 New Bulgaria 2 (+1) India 1 Serbia 1 China 2 New Ireland 1 Slovakia 2 Cyprus 1 Israel 1 Slovenia 3 Croatia 3 Italy 24 Spain 28 (+3) Czech Republic 3 (+1) Latvia 1 Sweden 2 Denmark 2 Lithuania 1 Switzerland 3 (-1) Estonia 2 Luxembourg 2 (+1) The Netherlands 2 Finland 2 Malta 2 (-1) Turkey 1 France 10 (+1) Morocco 1 New United Kingdom 4 Norway 1 Uruguay 1 Total No. of Labs = 175 Germany 25 (+2) Poland 11 (+2) Total No. of non EU/EFTA Labs = 13 4 th Joint Workshop of the European Union Reference Laboratories Total forno. Residues of Countries of Pesticides = 40

5 Participation Total No. of Labs = 175 EU/EFTA Labs = 162 Other countries Labs = 13 Total No. of Countries = 40 EU/EFTA countries = 30 Other countries = 10 (27 EU + 3 EFTA + 1 acceding country* + 2 Candidate countries + 7 other countries) *Although it is now an EU member state, Croatia was acceding country when the exercise took place

6 Clofentezine Fenarimol Lambda-Cyhalothrin Phosmet oxon 3-hydroxy-carbofuran Clothianidin Fenazaquin Linuron Phoxim Acephate Cyfluthrin Fenbuconazole Lufenuron Pirimicarb Acetamiprid Cypermethrin Fenhexamid Malaoxon Pirimiphos-methyl Acrinathrin Cyproconazole Fenitrothion Malathion Prochloraz Aldicarb Cyprodinil Fenoxycarb Mepanipyrim Procymidone Aldicarb Sulfone Deltamethrin Fenpropathrin Metaflumizone* Profenofos Aldicarb Sulfoxide Demeton-S-methylsulfone Fenpropimorph Metalaxyl and metalaxyl-m Propargite Amitraz Desmethyl-pirimicarb Fenthion Metconazole Propiconazole Azinphos-methyl Diazinon Fenthion oxon Methamidophos Propyzamide Azoxystrobin Dichlofluanid Fenthion oxon sulfone Methidathion Prothioconazole Benfuracarb Dichlorvos Fenthion oxon sulfoxide Methiocarb Prothiofos Bifenthrin Dicloran Fenthion sulfone Methiocarb sulfone Pyraclostrobin Bitertanol Dicofol Fenthion sulfoxide Methiocarb sulfoxide Pyridaben Boscalid Difenoconazole Fipronil Methomyl Pyrimethanil Bromopropylate Diflubenzuron Fludioxonil Methoxyfenozide Pyriproxyfen Bromuconazole Dimethoate Flufenoxuron Monocrotophos Quinoxyfen Spinosad Bupirimate Dimethomorph Fluopicolide* Myclobutanil Spirodiclofen Thiophanate-me Buprofezin DMST Fluquinconazole Omethoate Spiroxamine Tolclofos-methyl Cadusafos* Diphenylamine Flusilazole Orthophenylphenol Tau-Fluvalinate Tolylfluanid Captan DMF Flutolanil* Oxadixyl Tebuconazole Triadimefon Carbaryl DMPF Flutriafol Oxamyl Tebufenozide Triadimenol Carbendazim Endosulfan alpha Folpet Oxydemeton-methyl Tebufenpyrad Triazophos Carbofuran Endosulfan beta Fosthiazate Paclobutrazole Teflubenzuron Trichlorfon Carbosulfan Endosulfan sulfate Hexaconazole Paraoxon-methyl Tefluthrin Trifloxystrobin Chlorfenapyr EPN Hexythiazox Parathion-ethyl Tetraconazole Triflumuron Chlorfenvinphos Epoxiconazole Imazalil Parathion-methyl Tetradifon Trifluralin Chlorobenzilate* Ethion Imidacloprid Penconazole Thiabendazole Triticonazole Chlorothalonil Ethoprophos Indoxacarb Pencycuron Thiacloprid Vinclozolin Chlorpropham Etofenprox Iprodione Pendimethalin Thiamethoxam Zoxamide Chlorpyrifos Fenamiphos Iprovalicarb Phenthoate Thiodicarb Chlorpyrifos-methyl 4 Fenamiphos sulfone Isofenphos-methyl Phosalone Joint Workshop of the European Union Reference Laboratories for Residues of Pesticides *Not in the coordinated Fenamiphos sulfoxide Kresoxim-methyl Phosmet multiannual control programme 175 pesticides

7 Acephate Almería 23 rd -25 th October 2013 Pesticides used for the treatment Linuron * Not in the coordinated multiannual control programme Azoxystrobin Chlorpropham Chlorothalonil Cypermethrin Diazinon Fluopicolide* Methiocarb Pencycuron Prochloraz Procymidone Spirodiclofen Thiabendazole New in the target list Flutolanil* Fosthiazate Iprovalicarb Thiacloprid Total: 18 * COMMISSION IMPLEMENTING REGULATION (EU) No 788/2012 of 31 August 2012 concerning a coordinated multiannual control programme of the Union for 2013, 2014 and 2015 to ensure compliance with maximum residue levels of pesticides and to assess the consumer exposure to pesticide residues in and on food of plant and 4 th Joint Workshop of the European Union Reference Laboratories for animal Residues origin. of Pesticides

8 CALENDAR ACTIVITY DATE - Publishing the Target Pesticide List, Calendar on the Web page 22nd October Receiving Application Form from invited laboratories. 3rd Dec th Jan Specific Protocol published on the Web site 7th Jan 2013 at the latest - Filling in the Laboratory Scope from the Participants: Form 0 8th-18th January Sample distribution. 21st January Deadline for receiving sample acceptance: Form 1 25th January Deadline for receiving results: Form 2, Form 3 and Form 4 13th February Filling in Form 5 20th-27th February Preliminary Report: provisional results, medians and z-scores. April Final Report to the Laboratories December 2013

9 WEB PAGE: Forms

11 Potato

12 Organic Potatoes were grown in Almería, Spain

13 Post harvest treatment with commercial formulation and with standard solution

14 EUPT-FV15 Results 4 th Joint Workshop of the European Commercial Union Reference products Laboratories used to treat the sample EURL-FV Pesticide Concentration (mg/kg) MRRL Type Commercial Product Acephate < Standard Dr.Ehrenstorfer Azoxystrobin Commercial Ortiva 25% P/V Chlorpropham > Standard Sigma-Aldrich Chlorothalonil Commercial Bravo 50 Cypermethrin < Commercial Citron 10% Diazinon Commercial Fegazinongole 60% Fluopicolide < Standard Sigma-Aldrich Flutolanil Standard ChemService Fosthiazate < Commercial Nemathorin 10 G Iprovalicarb < Standard Sigma-Aldrich Linuron < Standard Sigma-Aldrich Methiocarb Standard Dr.Ehrenstorfer Pencycuron Commercial Trotis 25 sc Prochloraz < Standard Sigma-Aldrich Procymidone < Commercial Driza 50% Spirodiclofen Standard Sigma-Aldrich Thiabendazole > Commercial Textar 60T Thiacloprid Commercial Calypso 48% P/V

15 EUPT-FV15 Results 4 th Joint Workshop of the European Commercial Union Reference products Laboratories used to treat the sample EURL-FV Pesticide Concentration (mg/kg) MRRL Type Commercial Product Acephate < Standard Dr.Ehrenstorfer Azoxystrobin Commercial Ortiva 25% P/V Chlorpropham > Standard Sigma-Aldrich Chlorthalonil Commercial Bravo 50 Cypermethrin < Commercial Citron 10% Diazinon Commercial Fegazinongole 60% Fluopicolide < Standard Sigma-Aldrich Flutolanil Standard ChemService Fosthiazate < Commercial Nemathorin 10 G Iprovalicarb < Standard Sigma-Aldrich Linuron < Standard Sigma-Aldrich Methiocarb Standard Dr.Ehrenstorfer Pencycuron Commercial Trotis 25 sc Prochloraz < Standard Sigma-Aldrich Procymidone < Commercial Driza 50% Spirodiclofen Standard Sigma-Aldrich Thiabendazole > Commercial Textar 60T Thiacloprid Commercial Calypso 48% P/V

18 Homogeneity - The homogeneity in the treated sample was studied using the 2006 Harmonised Protocol. -The sampling standard deviation of all the pesticides must be lower than the critical value. S sample2 < c 20 extracts

19 Pesticide Almería 23 rd -25 th October 2013 Mean Conc. (mg/kg) Homogeneity All the pesticides passed the homogeneity test Ss 2 c Ss 2 < c Pass/Fail Acephate x x 10-5 Pass Azoxystrobin x x 10-4 Pass Chlorothalonil x x 10-4 Pass Chlorpropham x x 10-2 Pass Cypermethrin x x 10-4 Pass Diazinon x x 10-4 Pass Fluopicolide x x 10-4 Pass Flutolanil x x 10-3 Pass Fosthiazate x x 10-5 Pass Iprovalicarb x x 10-5 Pass Linuron x x 10-4 Pass Methiocarb x x 10-4 Pass Pencycuron x x 10-3 Pass Prochloraz x x 10-5 Pass Procymidone x x 10-4 Pass Spirodiclofen x x 10-3 Pass Thiabendazole x x 10-2 Pass Thiacloprid x x 10-3 Pass

20 Homogeneity Pesticide Mean Conc. Homogeneity (mg/kg) Assigned value (mg/kg) Difference (%) Acephate Azoxystrobin Chlorothalonil Chlorpropham Cypermethrin Diazinon Fluopicolide Flutolanil Fosthiazate Iprovalicarb Linuron Methiocarb Pencycuron ,4 Prochloraz ,2 Procymidone ,1 Spirodiclofen ,4 Thiabendazole ,9 Thiacloprid 4 th Joint Workshop of the European 0.364Union Reference Laboratories for Residues of -7,7 Pesticides

21 Stability 1 st Analysis - prior to the sample shipment 2 nd Analysis - after the deadline for reporting results

22 Stability Concentration (mg/kg) Pesticide Day 1 (1 st analysis) Day 1 (2 nd analysis) Mean 1 Day 2 (1 st analysis) Day 2 (2 nd analysis) Mean 2 (M2-M1) M1 % Acephate Azoxystrobin Chlorothalonil Chlorpropham Cypermethrin All the pesticides passed the stability test Diazinon Fluopicolide Flutolanil Fosthiazate Iprovalicarb Linuron Methiocarb Pencycuron Prochloraz Procymidone Spirodiclofen Thiabendazole Thiacloprid

23 Stability Additionally: 3 rd Analysis - reproducing the delivery conditions that the samples experienced during 48 hours

24 Stability Pesticide Day 1 (1 st analysis) Day 1 (2 nd analysis) Mean 1 Concentration (mg/kg) 48h (1 st analysis) 48h (2 nd analysis) Mean 2 (M2-M1) M1 Acephate Azoxystrobin Chlorothalonil Chlorpropham Cypermethrin All the pesticides passed the stability test Diazinon Fluopicolide Flutolanil Fosthiazate Iprovalicarb Linuron Methiocarb Pencycuron Prochloraz Procymidone Spirodiclofen Thiabendazole Thiacloprid %

25 100ppb_Mix FV15_Potato Almería 23 rd -25 th October 2013 Spirodiclofen correct storage conditions 400ppb_Spirodiclofen_Potato 400ppb_Spirodiclofen_Solvent Spirodiclofen [M+H] + : C 21 H 24 Cl 2 O 4 Sample_189_FV15 100ppb_Mix FV15_Potato Sample_189_FV15

26 3-OH-Spirodiclofen-enol C 15 H 14 Cl 2 O 4 [M+H]+: Spirodiclofen sample after 4 days at room temperature Spirodiclofen-enol C 15 H 14 Cl 2 O 3 [M+H]+: Sample_189 Spirodiclofen C 21 H 24 Cl 2 O 4 [M+H] + : Spirodiclofen C 21 H 24 Cl 2 O 4 [M+H] + :

27 Spirodiclofen Spirodiclofen-enol 3-hydroxy-spirodiclofen-enol

28 PROCHLORAZ- Potato sample at room temperature during 4 days Prochloraz metabolite C 11 H 14 NOCl 3 [M+H]+: Prochloraz C 15 H 17 N 3 O 2 Cl 3 [M+H]+: Sample 189 Day 1 Sample 189 Day 4 room temp. Sample 189 Day 4 room temp. Sample 189 Day 1

29 RESULTS

30 Distribution of data-histograms Acephate Azoxystrobin Frequency Frequency ,03 0,06 0,09 0,12 0,15 mg/kg Median: mg/kg Median: mg/kg mg/kg Chlorothalonil Chlorpropham Frequency Frequency mg/kg Median: mg/kg mg/kg Median: mg/kg

31 Distribution of data-histograms Cypermethrin Diazinon Frequency Frequency ,02 0,08 0,18 0,28 0,38 50 Median: mg/kg Fluopicolide mg/kg mg/kg Median: mg/kg Flutolanil Frequency Frequency ,03 0,06 0,09 0,12 0,15 0,18 Median: mg/kg mg/kg mg/kg Median: mg/kg

32 Distribution of data-histograms Iprovalicarb Linuron Frequency Frequency mg/kg Median: mg/kg 0 0 0,03 0,06 0,09 0,12 0,15 0,18 Median: mg/kg mg/kg Methiocarb Pencycuron Frequency Frequency mg/kg Median: mg/kg Median: mg/kg mg/kg

33 Distribution of data-histograms Prochloraz Procymidone Frequency Frequency ,02 0,04 0,06 0,08 0,1 Median: mg/kg mg/kg 0 0 0,04 0,08 0,12 0,16 0,2 0,24 Median: mg/kg mg/kg Spirodiclofen Thiabendazole Frequency Frequency mg/kg Median: mg/kg Median: mg/kg mg/kg

34 Distribution of data-histograms Fosthiazate 50 Frequency mg/kg Median: mg/kg Thiacloprid Frequency ,2 0,4 0,6 0,8 Median: mg/kg mg/kg

35 Pesticides Almería 23 rd -25 th October 2013 Median (mg/kg) Prochloraz Fosthiazate Acephate Iprovalicarb Linuron Fluopicolide Cypermethrin Procymidone Methiocarb Chlorothalonil Diazinon Azoxystrobin Pencycuron Thiacloprid Flutolanil Spirodiclofen Chlorpropham Thiabendazole 1.710

36 Pesticides Almería 23 rd -25 th October 2013 Median (mg/kg) Prochloraz Fosthiazate Acephate Iprovalicarb Linuron Fluopicolide Cypermethrin Procymidone Methiocarb Chlorothalonil Diazinon Azoxystrobin Pencycuron Thiacloprid Flutolanil Spirodiclofen Chlorpropham Thiabendazole mg/kg

37 Pesticides Almería 23 rd -25 th October 2013 Median (mg/kg) Prochloraz Fosthiazate Acephate Iprovalicarb Linuron Fluopicolide Cypermethrin Procymidone Methiocarb Chlorothalonil Diazinon Azoxystrobin Pencycuron Thiacloprid Flutolanil Spirodiclofen Chlorpropham Thiabendazole mg/kg mg/kg

38 Pesticides Almería 23 rd -25 th October 2013 Median (mg/kg) Prochloraz Fosthiazate Acephate Iprovalicarb Linuron Fluopicolide Cypermethrin Procymidone Methiocarb Chlorothalonil Diazinon Azoxystrobin Pencycuron Thiacloprid Flutolanil Spirodiclofen Chlorpropham Thiabendazole mg/kg mg/kg mg/kg

39 Pesticides MRRL (mg/kg) Median (mg/kg) FFP RSD (%) Qn RSD (%) Acephate Azoxystrobin Chlorothalonil Chlorpropham Cypermethrin Diazinon Fluopicolide Flutolanil Fosthiazate Iprovalicarb Linuron Methiocarb Pencycuron Prochloraz Procymidone Spirodiclofen Thiabendazole Thiacloprid 4 th Joint Workshop of the 0.01 European Union Reference Laboratories for Residues 25of Pesticides 18.4

40 % Almería 23 rd -25 th October 2013 Robust standard deviations

41 Pesticides Almería No. 23 rd of -25 th October No. 2013of False Reported Negative Results Results No. of Not Analysed Results Percentage of Reported Results (out of 160) Acephate Azoxystrobin Chlorothalonil Chlorpropham Cypermethrin Diazinon Fluopicolide Flutolanil Fosthiazate Iprovalicarb Linuron Methiocarb Pencycuron Prochloraz Procymidone Spirodiclofen Thiabendazole Thiachloprid 4 th Joint Workshop of 121 the European Union Reference 2 Laboratories 37 for Residues of Pesticides 76

42 z-scores

43 z-scores classification % Acceptable Questionable Unacceptable

44 Pesticides Median (mg/kg) Almería 23 rd -25 th October 2013 Acceptable (%) Questionable Unacceptable (%) (%) Acephate Azoxystrobin Chlorothalonil Chlorpropham Cypermethrin Diazinon Fluopicolide Flutolanil Fosthiazate Iprovalicarb Linuron Methiocarb Pencycuron Prochloraz Procymidone Spirodiclofen Thiabendazole Thiacloprid 4 th Joint Workshop of the European Union Reference 95.0 Laboratories for 2.5Residues of Pesticides 2.5

45 Pesticides Median (mg/kg) Almería 23 rd -25 th October 2013 Acceptable (%) Questionable Unacceptable (%) (%) Acephate Azoxystrobin Chlorothalonil Chlorpropham Cypermethrin Diazinon Fluopicolide Flutolanil Fosthiazate Iprovalicarb Linuron Methiocarb Pencycuron Prochloraz Procymidone Spirodiclofen Thiabendazole Thiacloprid 4 th Joint Workshop of the European Union Reference 95.0 Laboratories for 2.5Residues of Pesticides 2.5

46 Acephate Median: mg/kg Acceptable Questionable Unacceptable 90% 4% 6% Lab019 Lab010 Lab086 Lab049 Lab006 Lab079 Lab128 Lab095 Lab045 Lab037 Lab022 Lab085 Lab154 Lab116 Lab099 Lab080 Lab005 Lab131 Lab002 Lab138 Lab126 Lab119 Lab094 Lab092 Lab120 Lab104 Lab144 Lab018 Lab163 Lab112 Lab075 Lab046 Lab030 Lab161 Lab107 Lab083 Lab121 Lab158 Lab033 Lab156 Lab118 Lab111 Lab068 Lab039 Lab052 Lab044 Lab078 Lab054 Lab043 Lab004 Lab135 Lab132 Lab093 Lab047 Lab014 Lab136 Lab026 Lab130 Lab103 Lab038 Lab029 Lab165 Lab100 Lab073 Lab062 Lab082 Lab059 Lab057 Lab067 Lab123 Lab097 Lab076 Lab008 Lab159 Lab108 Lab110 Lab105 Lab117 Lab051 Lab024 Lab140 Lab101 Lab066 Lab007 Lab114 Lab015 Lab069 Lab061 Lab053 Lab137 Lab109 Lab162 Lab072 Lab173 Lab125 Lab032 Lab027 Lab013 Lab011 Lab166 Lab050 Lab171 Lab143 Lab134 Lab017 Lab065 Lab058 Lab028 Lab012 Lab090 Lab055 Lab172 Lab034 Lab025 Lab106 Lab129 Lab020 Lab035 Lab074 Lab102 Lab021 Lab160 Lab001 Lab150 Lab147 Lab145 Lab089 Lab087 Lab084 Lab077 Lab064 Lab L L L L L L L L L L L L ** ****** or L LC or G GC or B Both * False Negatives

47 y Azoxystrobin Median: mg/kg Acceptable Questionable Unacceptable 98% 1% 1% Lab010 Lab085 Lab037 Lab077 Lab046 Lab055 Lab062 Lab101 Lab107 Lab026 Lab014 Lab047 Lab132 Lab092 Lab076 Lab064 Lab163 Lab083 Lab067 Lab042 Lab127 Lab053 Lab128 Lab104 Lab082 Lab003 Lab173 Lab121 Lab119 Lab120 Lab103 Lab102 Lab021 Lab140 Lab066 Lab171 Lab019 Lab161 Lab142 Lab057 Lab048 Lab160 Lab158 Lab145 Lab130 Lab129 Lab110 Lab109 Lab099 Lab095 Lab030 Lab043 Lab065 Lab009 Lab144 Lab093 Lab022 Lab097 Lab075 Lab059 Lab149 Lab105 Lab135 Lab156 Lab150 Lab118 Lab108 Lab136 Lab024 Lab080 Lab005 Lab159 Lab151 Lab054 Lab063 Lab038 Lab028 Lab165 Lab034 Lab139 Lab086 Lab069 Lab068 Lab061 Lab044 Lab039 Lab036 Lab029 Lab011 Lab168 Lab058 Lab146 Lab134 Lab020 Lab143 Lab088 Lab052 Lab007 Lab157 Lab138 Lab126 Lab125 Lab111 Lab045 Lab035 Lab012 Lab074 Lab017 Lab049 Lab137 Lab114 Lab051 Lab050 Lab141 Lab131 Lab113 Lab060 Lab018 Lab013 Lab006 Lab001 Lab096 Lab154 Lab073 Lab004 Lab166 Lab089 Lab025 Lab008 Lab123 Lab070 Lab015 Lab072 Lab100 Lab112 Lab002 Lab079 Lab133 Lab033 Lab098 Lab106 Lab094 Lab090 Lab032 Lab116 Lab172 Lab153 Lab117 Lab078 Lab016 Lab084 Lab L LG L LGGLGGL LGG L L L L B or L LC or G GC or B Both * * False Negatives

48 Chlorothalonil Median: mg/kg Acceptable Questionable Unacceptable 84% 7% 9% Lab129 Lab075 Lab043 Lab004 Lab108 Lab102 Lab158 Lab026 Lab088 Lab135 Lab031 Lab019 Lab052 Lab171 Lab029 Lab098 Lab073 Lab140 Lab161 Lab033 Lab173 Lab142 Lab028 Lab144 Lab109 Lab049 Lab038 Lab024 Lab139 Lab092 Lab087 Lab074 Lab103 Lab067 Lab105 Lab030 Lab020 Lab048 Lab003 Lab143 Lab095 Lab061 Lab021 Lab166 Lab096 Lab146 Lab104 Lab101 Lab131 Lab080 Lab066 Lab046 Lab055 Lab017 Lab156 Lab154 Lab151 Lab113 Lab111 Lab110 Lab086 Lab037 Lab058 Lab042 Lab059 Lab163 Lab082 Lab022 Lab145 Lab107 Lab093 Lab079 Lab070 Lab018 Lab065 Lab063 Lab152 Lab150 Lab138 Lab119 Lab069 Lab064 Lab060 Lab035 Lab011 Lab132 Lab039 Lab120 Lab034 Lab160 Lab133 Lab094 Lab077 Lab115 Lab099 Lab009 Lab012 Lab078 Lab117 Lab005 Lab123 Lab121 Lab044 Lab016 Lab097 Lab054 Lab050 Lab147 Lab112 Lab007 Lab008 Lab002 Lab062 Lab032 Lab116 Lab172 Lab085 Lab118 Lab114 Lab025 Lab090 Lab015 Lab165 Lab137 Lab125 Lab068 Lab106 Lab051 Lab013 Lab053 Lab136 Lab159 Lab149 Lab084 Lab153 Lab134 Lab083 Lab027 Lab GGGGGLGGGGGG or L LC or G GC or B Both ***** * False Negatives

49 Chlorpropham Median: mg/kg Acceptable Questionable Unacceptable 93% 3% 4% L GGGGGGGL GGG Lab095 Lab008 Lab104 Lab072 Lab089 Lab012 Lab064 Lab016 Lab151 Lab052 Lab107 Lab037 Lab070 Lab014 Lab101 Lab116 Lab075 Lab006 Lab140 Lab026 Lab099 Lab079 Lab158 Lab080 Lab076 Lab059 Lab058 Lab021 Lab035 Lab065 Lab156 Lab068 Lab033 Lab027 Lab043 Lab130 Lab047 Lab067 Lab154 Lab132 Lab093 Lab024 Lab125 Lab048 Lab004 Lab011 Lab161 Lab062 Lab005 Lab007 Lab119 Lab077 Lab042 Lab172 Lab049 Lab019 Lab066 Lab103 Lab054 Lab173 Lab097 Lab163 Lab127 Lab147 Lab138 Lab120 Lab139 Lab129 Lab121 Lab111 Lab110 Lab102 Lab029 Lab094 Lab149 Lab135 Lab030 Lab046 Lab136 Lab017 Lab171 Lab150 Lab061 Lab051 Lab036 Lab028 Lab146 Lab050 Lab022 Lab082 Lab092 Lab112 Lab078 Lab020 Lab034 Lab137 Lab134 Lab141 Lab109 Lab018 Lab001 Lab118 Lab074 Lab168 Lab032 Lab073 Lab013 Lab143 Lab053 Lab090 Lab015 Lab025 Lab108 Lab039 Lab106 Lab166 Lab165 Lab055 Lab063 Lab038 Lab044 Lab131 Lab100 Lab002 Lab088 Lab145 Lab123 Lab105 Lab142 Lab114 Lab057 Lab003 Lab153 Lab010 Lab160 Lab085 Lab or L LC or G GC or B Both ** * * False Negatives

50 Cypermethrin Median: mg/kg Acceptable Questionable Unacceptable 89% 6% 5% GGGGL LGGGGG Lab027 Lab026 Lab138 Lab089 Lab059 Lab070 Lab037 Lab144 Lab101 Lab049 Lab004 Lab140 Lab109 Lab055 Lab066 Lab080 Lab150 Lab130 Lab086 Lab076 Lab054 Lab052 Lab098 Lab042 Lab135 Lab093 Lab043 Lab020 Lab132 Lab141 Lab139 Lab129 Lab126 Lab119 Lab112 Lab061 Lab029 Lab102 Lab067 Lab039 Lab104 Lab088 Lab017 Lab105 Lab097 Lab058 Lab035 Lab021 Lab168 Lab128 Lab121 Lab111 Lab110 Lab118 Lab025 Lab173 Lab127 Lab143 Lab024 Lab005 Lab142 Lab063 Lab171 Lab062 Lab048 Lab159 Lab120 Lab099 Lab008 Lab152 Lab125 Lab113 Lab074 Lab044 Lab028 Lab018 Lab108 Lab096 Lab019 Lab078 Lab073 Lab069 Lab047 Lab036 Lab166 Lab030 Lab034 Lab161 Lab116 Lab065 Lab158 Lab154 Lab115 Lab103 Lab068 Lab060 Lab015 Lab051 Lab149 Lab147 Lab022 Lab095 Lab079 Lab038 Lab123 Lab075 Lab007 Lab114 Lab012 Lab146 Lab085 Lab156 Lab106 Lab087 Lab172 Lab151 Lab107 Lab160 Lab090 Lab050 Lab046 Lab001 Lab134 Lab117 Lab100 Lab092 Lab157 Lab133 Lab145 Lab013 Lab165 Lab009 Lab163 Lab011 Lab033 Lab053 Lab137 Lab084 Lab071 Lab094 Lab057 Lab136 Lab032 Lab170 Lab010 Lab153 Lab083 Lab077 Lab072 Lab064 Lab006 Lab ****** or L LC or G GC or B Both * False Negatives

51 Diazinon Median: mg/kg Acceptable Questionable Unacceptable 95% 3% 2% Lab098 Lab109 Lab095 Lab006 Lab045 Lab021 Lab052 Lab037 Lab031 Lab016 Lab161 Lab014 Lab043 Lab096 Lab140 Lab026 Lab004 Lab035 Lab154 Lab010 Lab132 Lab163 Lab162 Lab076 Lab024 Lab104 Lab020 Lab103 Lab101 Lab130 Lab127 Lab107 Lab102 Lab083 Lab075 Lab080 Lab105 Lab066 Lab059 Lab120 Lab099 Lab038 Lab119 Lab108 Lab086 Lab065 Lab128 Lab116 Lab022 Lab173 Lab147 Lab093 Lab088 Lab078 Lab142 Lab129 Lab125 Lab110 Lab068 Lab029 Lab135 Lab115 Lab089 Lab097 Lab168 Lab063 Lab106 Lab058 Lab158 Lab156 Lab144 Lab139 Lab121 Lab113 Lab111 Lab074 Lab055 Lab082 Lab042 Lab067 Lab143 Lab117 Lab054 Lab030 Lab051 Lab007 Lab092 Lab062 Lab047 Lab171 Lab141 Lab138 Lab069 Lab064 Lab060 Lab033 Lab149 Lab002 Lab118 Lab079 Lab005 Lab036 Lab048 Lab019 Lab160 Lab150 Lab094 Lab027 Lab018 Lab011 Lab166 Lab017 Lab146 Lab085 Lab028 Lab172 Lab131 Lab012 Lab034 Lab008 Lab152 Lab145 Lab126 Lab073 Lab070 Lab044 Lab015 Lab001 Lab134 Lab009 Lab039 Lab049 Lab072 Lab137 Lab151 Lab046 Lab123 Lab112 Lab050 Lab165 Lab025 Lab159 Lab084 Lab061 Lab032 Lab100 Lab090 Lab133 Lab157 Lab136 Lab087 Lab013 Lab057 Lab053 Lab003 Lab077 Lab153 Lab170 Lab GGGLGGGGLG or L LC or G GC or B Both * False Negatives

52 Fluopicolide Median: mg/kg Acceptable Questionable Unacceptable 96% 4% 0% Lab110 Lab026 Lab010 Lab080 Lab138 Lab109 Lab145 Lab037 Lab057 Lab062 Lab107 Lab092 Lab004 Lab104 Lab047 Lab055 Lab048 Lab005 Lab073 Lab054 Lab132 Lab131 Lab083 Lab065 Lab156 Lab045 Lab043 Lab171 Lab149 Lab059 Lab049 Lab165 Lab079 Lab030 Lab102 Lab052 Lab034 Lab097 Lab075 Lab020 Lab121 Lab119 Lab111 Lab086 Lab064 Lab035 Lab028 Lab067 Lab038 Lab163 Lab143 Lab136 Lab108 Lab074 Lab044 Lab012 Lab007 Lab120 Lab066 Lab042 Lab103 Lab093 Lab046 Lab068 Lab024 Lab150 Lab118 Lab099 Lab017 Lab011 Lab106 Lab029 Lab022 Lab061 Lab025 Lab105 Lab100 Lab018 Lab008 Lab129 Lab112 Lab123 Lab002 Lab173 Lab015 Lab161 Lab166 Lab050 Lab051 Lab039 Lab013 Lab137 Lab090 Lab078 Lab G G L L G L G G G G L G L L G L L or L LC or G GC or B Both * False Negatives

53 Flutolanil Median: mg/kg Acceptable Questionable Unacceptable 96% 2% 2% G L G G G L G L L L L L L G Lab010 Lab045 Lab037 Lab080 Lab026 Lab163 Lab033 Lab136 Lab055 Lab073 Lab092 Lab038 Lab079 Lab143 Lab156 Lab095 Lab006 Lab049 Lab046 Lab043 Lab057 Lab065 Lab110 Lab005 Lab107 Lab132 Lab171 Lab119 Lab064 Lab149 Lab075 Lab097 Lab034 Lab021 Lab020 Lab145 Lab138 Lab109 Lab059 Lab058 Lab007 Lab102 Lab120 Lab042 Lab121 Lab111 Lab044 Lab129 Lab066 Lab061 Lab029 Lab104 Lab093 Lab078 Lab103 Lab035 Lab004 Lab173 Lab067 Lab068 Lab017 Lab100 Lab030 Lab106 Lab002 Lab013 Lab028 Lab024 Lab118 Lab052 Lab011 Lab099 Lab094 Lab062 Lab105 Lab022 Lab018 Lab054 Lab112 Lab050 Lab108 Lab086 Lab074 Lab001 Lab012 Lab166 Lab096 Lab051 Lab137 Lab025 Lab015 Lab008 Lab072 Lab165 Lab161 Lab039 Lab090 Lab123 Lab084 Lab or L LC or G GC or B Both * * False Negatives

54 Fosthiazate Median: mg/kg Acceptable Questionable Unacceptable 96% 2% 2% Lab027 Lab084 Lab077 Lab045 Lab010 Lab118 Lab021 Lab110 Lab037 Lab092 Lab107 Lab064 Lab109 Lab026 Lab052 Lab038 Lab073 Lab030 Lab005 Lab163 Lab161 Lab120 Lab104 Lab006 Lab099 Lab078 Lab076 Lab022 Lab121 Lab119 Lab136 Lab057 Lab044 Lab004 Lab083 Lab033 Lab017 Lab095 Lab039 Lab165 Lab145 Lab080 Lab059 Lab108 Lab101 Lab020 Lab171 Lab111 Lab103 Lab074 Lab067 Lab013 Lab097 Lab075 Lab009 Lab172 Lab066 Lab034 Lab132 Lab093 Lab079 Lab065 Lab055 Lab018 Lab137 Lab068 Lab043 Lab024 Lab173 Lab061 Lab123 Lab102 Lab007 Lab166 Lab054 Lab015 Lab049 Lab012 Lab086 Lab112 Lab090 Lab035 Lab001 Lab062 Lab011 Lab105 Lab028 Lab051 Lab050 Lab129 Lab100 Lab046 Lab130 Lab106 Lab008 Lab029 Lab025 Lab082 Lab002 Lab156 Lab053 Lab G G G G G L L L G L L L G L L L L G L * or L LC or G GC or B Both * False Negatives

55 Iprovalicarb Median: mg/kg Acceptable Questionable Unacceptable 97.6% 1.6% 0.8% Lab027 Lab086 Lab085 Lab037 Lab026 Lab096 Lab053 Lab140 Lab109 Lab118 Lab021 Lab005 Lab136 Lab047 Lab022 Lab121 Lab107 Lab076 Lab033 Lab057 Lab055 Lab079 Lab038 Lab063 Lab159 Lab030 Lab163 Lab104 Lab083 Lab082 Lab048 Lab092 Lab052 Lab158 Lab156 Lab130 Lab126 Lab119 Lab110 Lab101 Lab064 Lab046 Lab132 Lab080 Lab019 Lab127 Lab067 Lab103 Lab059 Lab045 Lab012 Lab138 Lab157 Lab058 Lab160 Lab120 Lab099 Lab065 Lab061 Lab146 Lab097 Lab075 Lab068 Lab032 Lab020 Lab006 Lab151 Lab062 Lab100 Lab069 Lab066 Lab002 Lab150 Lab111 Lab093 Lab165 Lab108 Lab102 Lab049 Lab044 Lab043 Lab034 Lab143 Lab050 Lab007 Lab013 Lab004 Lab137 Lab018 Lab011 Lab173 Lab171 Lab145 Lab106 Lab105 Lab074 Lab024 Lab073 Lab039 Lab131 Lab035 Lab017 Lab161 Lab129 Lab054 Lab029 Lab015 Lab114 Lab166 Lab090 Lab001 Lab028 Lab123 Lab051 Lab010 Lab078 Lab112 Lab135 Lab025 Lab162 Lab072 Lab095 Lab008 Lab L L L L L L L L L L L L G L L L G L or L LC or G GC or B Both * False Negatives

56 Linuron Median: mg/kg Acceptable Questionable Unacceptable 95% 4% 1% Lab098 Lab052 Lab101 Lab021 Lab010 Lab080 Lab109 Lab037 Lab006 Lab002 Lab062 Lab064 Lab055 Lab057 Lab019 Lab128 Lab154 Lab067 Lab144 Lab140 Lab138 Lab107 Lab076 Lab001 Lab120 Lab083 Lab079 Lab047 Lab103 Lab165 Lab049 Lab038 Lab030 Lab158 Lab145 Lab141 Lab130 Lab121 Lab104 Lab068 Lab072 Lab065 Lab132 Lab059 Lab026 Lab005 Lab097 Lab053 Lab078 Lab139 Lab119 Lab108 Lab099 Lab093 Lab074 Lab022 Lab018 Lab157 Lab150 Lab095 Lab159 Lab110 Lab075 Lab044 Lab004 Lab105 Lab029 Lab163 Lab034 Lab151 Lab171 Lab046 Lab033 Lab135 Lab129 Lab111 Lab173 Lab058 Lab024 Lab118 Lab048 Lab045 Lab035 Lab162 Lab136 Lab102 Lab073 Lab032 Lab013 Lab137 Lab020 Lab017 Lab106 Lab086 Lab054 Lab043 Lab117 Lab100 Lab160 Lab114 Lab166 Lab172 Lab039 Lab015 Lab112 Lab088 Lab051 Lab094 Lab063 Lab028 Lab061 Lab025 Lab050 Lab153 Lab090 Lab161 Lab123 Lab096 Lab012 Lab007 Lab092 Lab008 Lab066 Lab011 Lab084 Lab156 Lab L L L L L L L L L L L L L L L L L L L L GG * or L LC or G GC or B Both * False Negatives

57 Methiocarb Median: mg/kg Acceptable Questionable Unacceptable 93% 2% 5% Lab077 Lab013 Lab098 Lab140 Lab085 Lab062 Lab156 Lab064 Lab033 Lab057 Lab105 Lab096 Lab080 Lab163 Lab048 Lab030 Lab052 Lab103 Lab072 Lab136 Lab130 Lab104 Lab037 Lab021 Lab128 Lab097 Lab047 Lab002 Lab107 Lab101 Lab076 Lab014 Lab006 Lab065 Lab083 Lab046 Lab026 Lab035 Lab038 Lab119 Lab110 Lab061 Lab165 Lab132 Lab059 Lab058 Lab082 Lab004 Lab055 Lab099 Lab079 Lab129 Lab121 Lab109 Lab108 Lab070 Lab045 Lab044 Lab043 Lab005 Lab001 Lab073 Lab039 Lab034 Lab137 Lab075 Lab120 Lab022 Lab154 Lab020 Lab050 Lab173 Lab158 Lab145 Lab126 Lab111 Lab095 Lab068 Lab066 Lab029 Lab028 Lab018 Lab118 Lab012 Lab017 Lab172 Lab149 Lab019 Lab171 Lab049 Lab159 Lab074 Lab024 Lab093 Lab106 Lab112 Lab092 Lab150 Lab123 Lab032 Lab114 Lab054 Lab100 Lab102 Lab025 Lab166 Lab069 Lab015 Lab011 Lab135 Lab051 Lab161 Lab146 Lab131 Lab086 Lab134 Lab151 Lab090 Lab027 Lab053 Lab007 Lab031 Lab067 Lab078 Lab008 Lab153 Lab160 Lab084 Lab138 Lab094 Lab060 Lab L L L L L L L L L L L L B L L L G or L LC or G GC or B Both **** * False Negatives

58 Pencycuron Median: mg/kg Acceptable Questionable Unacceptable 97% 2% 1% Lab010 Lab158 Lab021 Lab061 Lab118 Lab101 Lab062 Lab052 Lab104 Lab080 Lab037 Lab055 Lab030 Lab130 Lab121 Lab033 Lab120 Lab119 Lab085 Lab043 Lab004 Lab132 Lab076 Lab029 Lab006 Lab083 Lab057 Lab046 Lab067 Lab064 Lab059 Lab026 Lab099 Lab073 Lab129 Lab107 Lab044 Lab035 Lab038 Lab163 Lab054 Lab075 Lab034 Lab012 Lab135 Lab097 Lab093 Lab065 Lab173 Lab156 Lab138 Lab111 Lab108 Lab103 Lab095 Lab086 Lab068 Lab020 Lab019 Lab063 Lab088 Lab136 Lab145 Lab110 Lab074 Lab024 Lab013 Lab001 Lab092 Lab143 Lab082 Lab114 Lab149 Lab140 Lab005 Lab022 Lab105 Lab017 Lab102 Lab109 Lab066 Lab045 Lab137 Lab165 Lab002 Lab166 Lab025 Lab014 Lab011 Lab028 Lab049 Lab112 Lab094 Lab058 Lab008 Lab123 Lab078 Lab018 Lab015 Lab050 Lab106 Lab051 Lab161 Lab079 Lab100 Lab090 Lab157 Lab032 Lab007 Lab053 Lab084 Lab039 Lab L GG G L L L L L G L G L L L L L L or L LC or G GC or B Both * False Negatives

59 Prochloraz Median: mg/kg Acceptable Questionable Unacceptable 90% 8% 2% Lab080 Lab035 Lab110 Lab077 Lab070 Lab109 Lab085 Lab048 Lab141 Lab118 Lab037 Lab101 Lab055 Lab020 Lab014 Lab128 Lab171 Lab092 Lab029 Lab132 Lab104 Lab047 Lab130 Lab066 Lab026 Lab097 Lab168 Lab138 Lab088 Lab058 Lab030 Lab010 Lab083 Lab076 Lab061 Lab142 Lab140 Lab099 Lab054 Lab004 Lab001 Lab135 Lab119 Lab028 Lab039 Lab002 Lab154 Lab121 Lab173 Lab136 Lab129 Lab120 Lab021 Lab063 Lab106 Lab093 Lab074 Lab049 Lab036 Lab011 Lab017 Lab163 Lab086 Lab045 Lab043 Lab131 Lab105 Lab102 Lab158 Lab044 Lab108 Lab094 Lab143 Lab112 Lab082 Lab073 Lab062 Lab059 Lab161 Lab111 Lab025 Lab072 Lab057 Lab024 Lab022 Lab034 Lab033 Lab005 Lab157 Lab095 Lab038 Lab052 Lab152 Lab114 Lab107 Lab068 Lab064 Lab019 Lab006 Lab137 Lab098 Lab075 Lab166 Lab007 Lab103 Lab015 Lab172 Lab100 Lab160 Lab123 Lab046 Lab165 Lab065 Lab145 Lab018 Lab159 Lab008 Lab050 Lab051 Lab150 Lab069 Lab090 Lab067 Lab096 Lab013 Lab134 Lab113 Lab151 Lab032 Lab079 Lab009 Lab153 Lab156 Lab078 Lab133 Lab053 Lab L L GL L L L L L G L L L L L LG L G ** * or L LC or G GC or B Both * False Negatives

60 Procymidone Median: mg/kg Acceptable Questionable Unacceptable 95% 3% 2% Lab013 Lab086 Lab098 Lab064 Lab096 Lab135 Lab053 Lab037 Lab089 Lab154 Lab101 Lab130 Lab048 Lab052 Lab019 Lab043 Lab035 Lab059 Lab128 Lab003 Lab024 Lab147 Lab105 Lab062 Lab055 Lab095 Lab080 Lab079 Lab006 Lab132 Lab103 Lab104 Lab063 Lab021 Lab020 Lab026 Lab144 Lab118 Lab058 Lab078 Lab038 Lab004 Lab173 Lab168 Lab163 Lab158 Lab129 Lab125 Lab121 Lab119 Lab076 Lab075 Lab033 Lab031 Lab029 Lab016 Lab102 Lab030 Lab149 Lab088 Lab007 Lab072 Lab005 Lab136 Lab159 Lab143 Lab093 Lab067 Lab066 Lab065 Lab042 Lab142 Lab049 Lab171 Lab141 Lab139 Lab138 Lab111 Lab110 Lab109 Lab108 Lab107 Lab074 Lab068 Lab061 Lab047 Lab044 Lab027 Lab011 Lab010 Lab161 Lab017 Lab140 Lab034 Lab127 Lab106 Lab039 Lab097 Lab112 Lab092 Lab051 Lab036 Lab025 Lab120 Lab046 Lab028 Lab099 Lab054 Lab152 Lab150 Lab145 Lab134 Lab113 Lab094 Lab060 Lab018 Lab008 Lab002 Lab160 Lab146 Lab123 Lab057 Lab001 Lab117 Lab172 Lab073 Lab050 Lab137 Lab085 Lab157 Lab087 Lab077 Lab070 Lab015 Lab009 Lab100 Lab069 Lab082 Lab166 Lab114 Lab165 Lab116 Lab156 Lab032 Lab090 Lab022 Lab151 Lab131 Lab133 Lab084 Lab012 Lab170 Lab153 Lab GGGGGGG L GGGG GGGGGGGGGGGGGG or L LC or G GC or B Both * * False Negatives

61 Spirodiclofen Median: mg/kg Acceptable Questionable Unacceptable 91% 5% 5% Lab105 Lab088 Lab098 Lab062 Lab057 Lab104 Lab004 Lab043 Lab010 Lab037 Lab130 Lab052 Lab029 Lab026 Lab136 Lab030 Lab024 Lab080 Lab076 Lab163 Lab132 Lab137 Lab109 Lab143 Lab021 Lab092 Lab129 Lab033 Lab073 Lab049 Lab064 Lab048 Lab171 Lab138 Lab103 Lab059 Lab075 Lab112 Lab093 Lab158 Lab097 Lab061 Lab018 Lab102 Lab099 Lab011 Lab107 Lab045 Lab034 Lab150 Lab119 Lab067 Lab007 Lab055 Lab173 Lab111 Lab028 Lab100 Lab002 Lab054 Lab022 Lab095 Lab017 Lab065 Lab005 Lab110 Lab108 Lab068 Lab166 Lab145 Lab121 Lab074 Lab044 Lab012 Lab066 Lab114 Lab008 Lab025 Lab120 Lab082 Lab165 Lab051 Lab079 Lab006 Lab035 Lab123 Lab086 Lab046 Lab020 Lab015 Lab106 Lab013 Lab161 Lab090 Lab118 Lab096 Lab078 Lab085 Lab039 Lab050 Lab038 Lab149 Lab156 Lab084 Lab053 Lab083 Lab L L L L L L G GG L L L L L L L or L LC or G GC or B Both * * * False Negatives

62 Thiabendazole Median: mg/kg Acceptable Questionable Unacceptable 96% 3% 1% Lab095 Lab105 Lab136 Lab046 Lab006 Lab103 Lab037 Lab021 Lab098 Lab027 Lab173 Lab079 Lab083 Lab076 Lab068 Lab140 Lab080 Lab101 Lab163 Lab055 Lab033 Lab014 Lab099 Lab144 Lab151 Lab036 Lab100 Lab067 Lab165 Lab156 Lab123 Lab110 Lab109 Lab064 Lab026 Lab038 Lab075 Lab030 Lab059 Lab130 Lab019 Lab157 Lab005 Lab062 Lab145 Lab142 Lab104 Lab007 Lab093 Lab065 Lab008 Lab060 Lab058 Lab010 Lab153 Lab158 Lab121 Lab045 Lab029 Lab082 Lab135 Lab097 Lab128 Lab013 Lab017 Lab120 Lab072 Lab024 Lab150 Lab146 Lab138 Lab129 Lab119 Lab111 Lab090 Lab086 Lab077 Lab061 Lab018 Lab054 Lab159 Lab102 Lab047 Lab012 Lab049 Lab039 Lab137 Lab114 Lab034 Lab078 Lab044 Lab118 Lab053 Lab051 Lab057 Lab166 Lab043 Lab092 Lab066 Lab107 Lab015 Lab052 Lab143 Lab063 Lab025 Lab161 Lab112 Lab131 Lab125 Lab171 Lab002 Lab085 Lab050 Lab032 Lab084 Lab001 Lab028 Lab108 Lab035 Lab074 Lab011 Lab134 Lab096 Lab160 Lab069 Lab154 Lab094 Lab004 Lab106 Lab022 Lab020 Lab132 Lab073 Lab048 Lab L L L L L L L L L L L L L L L G L L G L L L or L LC or G GC or B Both * * False Negatives

63 Thiacloprid Median: mg/kg Acceptable Questionable Unacceptable 95.0% 2.5% 2.5% Lab039 Lab052 Lab037 Lab010 Lab140 Lab107 Lab030 Lab156 Lab128 Lab064 Lab055 Lab083 Lab038 Lab104 Lab080 Lab026 Lab002 Lab047 Lab079 Lab143 Lab005 Lab145 Lab007 Lab006 Lab163 Lab101 Lab046 Lab059 Lab043 Lab058 Lab121 Lab119 Lab109 Lab108 Lab086 Lab076 Lab018 Lab014 Lab099 Lab068 Lab057 Lab021 Lab130 Lab075 Lab072 Lab157 Lab022 Lab132 Lab120 Lab067 Lab008 Lab094 Lab065 Lab153 Lab033 Lab073 Lab097 Lab093 Lab110 Lab045 Lab136 Lab103 Lab165 Lab138 Lab111 Lab044 Lab013 Lab085 Lab066 Lab062 Lab054 Lab004 Lab082 Lab020 Lab024 Lab017 Lab134 Lab061 Lab051 Lab112 Lab090 Lab060 Lab035 Lab102 Lab118 Lab034 Lab137 Lab015 Lab173 Lab114 Lab166 Lab012 Lab028 Lab105 Lab092 Lab100 Lab158 Lab129 Lab032 Lab029 Lab001 Lab151 Lab135 Lab123 Lab161 Lab049 Lab154 Lab074 Lab025 Lab172 Lab011 Lab106 Lab095 Lab050 Lab069 Lab027 Lab078 Lab053 Lab150 Lab019 Lab162 Lab160 Lab L L L L L L L L L L L L L or L LC or G GC or B Both ** * False Negatives

64 Combined z-scores

65 Average of Squared z-scores 2 AZ 2 AZ 2 2 Good AZ 2 AZ 2 n i 1 Z i n Z 3 Satisfactory i 3 Unsatisfactory

66 NRLs OfLs AZ 2 Representation 92 % Good 7 % Satisfactory 1 % Unsatisfactory EU Laboratories Category A: 54 % of the EU/EFTA Laboratories (87 Laboratories out of 160) EUPT-FV14: 91 % Good 2 % Satisfactory 7 % Unsatisfactory

67 False Positives 6 different laboratories from EU/EFTA countries reported 6 pesticides as false positives

68 False Positives Laboratory Code Pesticide Concentration (mg/kg) Determination Technique RL (mg/kg) MRRL (mg/kg) Lab038 Captan GC-MSD (EI) ,01 Lab060 Dimethomorph LC-MS/MS (QQQ) (ESI+) Lab077 Carbendazim (sum of benomyl and carbendazim expressed as carbendazim) HPLC-FD Confirmation: GC- MS/MS (QQQ) (EI+) Lab114 Methiocarb sulfone LC-MS/MS (QQQ) (ESI+) Lab128 Fludioxonil LC-MS/MS (QQQ) Lab160 Tebuconazole LC-MS/MS (QQQ) (ESI+)

69 False Positives GC-MS or GC-MS/MS Captan Carbendazim LC-MS/MS or LC-FD Carbendazim Dimethomorph Fludioxonil Methiocarb sulfone Tebuconazole

70 Other detected pesticides Metabolites Methiocarb sulfoxide

71 Other detected pesticides Spiked with methiocarb Methiocarb Methiocarb sulfoxide mg/kg mg/kg

72 Other detected pesticides Methiocarb sulfoxide mg/kg Not used for the evaluation of the laboratories for statistical reasons

73 Other detected pesticides Impurities of commercial formulations

74 Other detected pesticides Spiked with diazinon Diazinon Sulfotep mg/kg Aprox mg/kg (NOT included in the target list)

75 LC-QTOF-MS Almería 23 rd -25 th October ppb_Sulfotep_Solvent Sample_60_SM05 Sulfotep [M+H] + : C 8 H 20 O 5 P 2 S 2 Sample_189_FV15

76 LC-QQQ-MS/MS 0.05 mg/kg Sulfotep in Potato matrix Sample EUPT- FV15_189A 323.1> >97.0 Ratio: 62 % Ratio: 63 % 323.1> >115.0

77 Other detected pesticides Contamination of comercial formulations

78 DIMETHOATE (Found in the sample at approx. 3 µg/kg) BLANK POTATO Std. 10 µg/kg POTATO SAMPLE 79A FV15 SRM1 230>125.1 SRM1 230>125.1 SRM1 230>125.1 SRM2 230>199.1 SRM2 SRM2 230> >199.1

79 DIMETHOATE (Found in the sample at approx. 3 µg/kg) BLANK POTATO Std. 10 µg/kg POTATO SAMPLE 79A FV15 SRM1 230>125.1 SRM1 230>125.1 SRM1 230>125.1 SRM2 230>199.1 SRM2 SRM2 230> >199.1

80 DIMETHOATE (Found in the sample at approx. 3 µg/kg) BLANK POTATO Std. 10 µg/kg POTATO SAMPLE 79A FV15 SRM1 230>125.1 SRM1 230>125.1 SRM1 230>125.1 SRM2 230>199.1 SRM2 SRM2 230> >199.1

81 DIMETHOATE (Found in the sample at approx. 3 µg/kg) BLANK POTATO Std. 10 µg/kg POTATO SAMPLE 79A FV15 SRM1 230>125.1 SRM1 230>125.1 SRM1 230>125.1 SRM2 230>199.1 SRM2 SRM2 230> >199.1

82 Endosulfan Almería 23 rd -25 th Alpha October 2013 (concentration < 10 µg/kg) 238.8>204 Std. 5 µg/kg Potato FV15 189A 241> > >160

83 Endosulfan Beta (concentration < 10 µg/kg) 241>206 Std. 5 µg/kg Potato FV15 189A 238.8> > >158.9

84 EUPT-FV15 Results EURL-FV 4 th Joint Workshop of the European Union Reference Laboratories

85 Evolution of the laboratories performance throughout the years Dispersion of results No.

86 Evolution of the laboratories performance throughout the years False Negatives %

of Pesticides in Target List 175 175 % of Labs in

87 Evolution of the laboratories performance throughout the years Labs in Category A No. of Pesticides in Target List % of Labs in Cat.A % % 51 % 51 % 45 % 56 % 52 % 52 %

88 Evolution of the laboratories performance Almería 23 throughout rd -25 October 2013 the years Labs in Category A EUPT-FV-07 EUPT-FV-13 EUPT-FV-14 EUPT-FV-15

89 Evolution of the laboratories performance throughout the years National Reference Laboratories No. Of NRLs with AZ 2 > 2 No. Of NRLs in Cat.B No.

90 Evolution of the laboratories performance throughout the years Common Pesticides Spirodiclofen Present in EUPT-FV14 New in EUPT-FV14 and EUPT-FV15 Target List Test Item % of Reported Results % of False Negative results EUPT FV EUPT FV % of z scores Acceptable Questionable Unacceptable EUPT FV EUPT FV

91 Evolution of the laboratories performance throughout the years Common Pesticides Thiabendazole % of z scores Acceptable Questionable Unacceptable EUPT FV EUPT FV EUPT FV

92 Evolution of the laboratories performance throughout the years Common Pesticides Iprodione % of z scores Acceptable Questionable Unacceptable EUPT FV EUPT FV EUPT FV

93 Conclusions Proficiency Tests are an efficient evaluation system, as they allow to follow the performance of the laboratories network. Throughout the years the results of the PTs have improved, although the laboratories should put their efforts into increasing the number of pesticides in their scope. The introduction of new pesticides in the target list provides an incentive for the laboratories to expand their scope.

94 Conclusions At least one laboratory from each Member State participated in EUPT-FV-15. Overall, the results were very good. Laboratories generally achieved accurate results for all the pesticides present in the test item. The concentration of the pesticides did not affect the results within the range of concentrations of this PT. No differences between the results obtained by different methods of analysis were observed.

95 Thank you for your Attention

EUPT-Panel. DG SANTE Mrs. Almut Bitterhof Mrs. Veerle Vanheusden

EUPT-Panel. DG SANTE Mrs. Almut Bitterhof Mrs. Veerle Vanheusden EUPT-FV17 Results ORGANISING GROUP Amadeo R. Fernández-Alba Milagros Mezcua Octavio Malato Carmen Ferrer STATISTICAL GROUP Carmelo Rodríguez QUALITY CONTROL GROUP Antonio Valverde Stewart Reynolds EUPT-Panel