General European Commission Proficiency Test Scheme EURL-FV Scientific Group Samples and Protocol INFORMATION EUPT Web Page Data Analysis Reports 1 2 3 4 5
ACTIVITY DATE Publishing the Calendar and Matrix on the EURL-FV Web page. 23 rd October 212 Submission of Application Form by invited laboratories. 3 rd Dec. 212-7th Jan 213 Sample distribution. 21 st January 212 Submission of sample receipt and acceptance - Form. Deadline for receiving results - Form1 As soon as sample is received 72 hours after receiving the sample Preliminary Report. March 213 Final Report distributed to the Laboratories. December 213
EUROPEAN PROFICIENCY TEST - FRUITS AND VEGETABLES - MASS SCREENING 4- Participants 17 NRLs* COUNTRY No. COUNTRY No. Austria 1* Italy 1*+5 Belgium 1*+2 Latvia 1* China 2 Romania 2* Croatia 1 Serbia 1 Czech Republic 1*+1 Slovenia 1* Denmark 1* Spain 6 Estonia 1* Sweden 1*+1 Finland 1* Switzerland 1*+1 France 1*+7 The Netherlands 1*+1 Germany 7 Turkey 1 Greece 1 UK 1*+2 Hungary 1*+2 58
58 EUPT-FV SCREENING METHODS 5 Participants with no results COUNTRY No. of laboratory Slovenia (results after the deadline) 3
Austria Belgium Czech Republic Denmark Estonia Finland France Germany Hungary Italy Latvia Netherlands Romania Slovenia Spain Sweden United Kingdom 18 Participating EU States Bulgaria Cyprus Greece Ireland Lithuania Luxembourg Malta Poland Portugal Slovakia China Croatia Serbia Switzerland Turkey 1 No Participating EU States 5 Participating Non EU States
Homogeneity test Test item No. 4 a 4 b 7 a 7 b 23 a 23 b 64 a 64 b 66 a 66 b 76 a 76 b 11 a 11 b 122 a 122 b 144 a 144 b 148 a 148 b A. Cc* (mg/kg) RSD (%) Aldicarb sulfone D D D D D D D D D D D D D D D D D D D D.21 14.7 Aldicarb Sulfoxide D D D D D D D D D D D D D D D D D D D D.426 9. Atrazine D D D D D D D D D D D D D D D D D D D D.31 1.2 Beta-Cyfluthrin D D D D D D D D D D D D D D D D D D D D.21 9.1 Bromoxynil D D D D D D D D D D D D D D D D D D D D.386 7.8 Clomazone D D D D D D D D D D D D D D D D D D D D.83 6.1 Dieldrin D D D D D D D D D D D D D D D D D D D D.4 6.4 Diuron D D D D D D D D D D D D D D D D D D D D.935 4.5 Fluazinam D D D D D D D D D D D D D D D D D D D D.3 13.6 Flufenacet D D D D D D D D D D D D D D D D D D D D.126 7.3 Metamitron D D D D D D D D D D D D D D D D D D D D.184 6.8 Methomyl# D D D D D D D D D D D D D D D D D D D D.37 9.4 Metribuzin D D D D D D D D D D D D D D D D D D D D.225 4.4 Molinate D D D D D D D D D D D D D D D D D D D D.6 12.3 Oxamyl D D D D D D D D D D D D D D D D D D D D.92 7.4 Picloram D D D D D D D D D D D D D D D D D D D D.98 13.1 Picolinafen D D D D D D D D D D D D D D D D D D D D.488 13.7 Propamocarb D D D D D D D D D D D D D D D D D D D D.82 7.7 Prosulfocarb D D D D D D D D D D D D D D D D D D D D.247 9.3 Quinoclamine D D D D D D D D D D D D D D D D D D D D.73 9.6 Thiodicarb# D D D D D D D D D D D D D D D D D D D D.68 1.1 Triflumizole D D D D D D D D D D D D D D D D D D D D.22 14.9 D: Detected A. Cc: Average Concentration RSD: Relative Standard Deviation (n=2) # Thiodicarb degradation product (not spiked) * Concentration evaluated by Organiser
The test material was spiked/treated with thiodicarb, which degrades to methomyl. The test material was not spiked/treated with methomyl. N S O O N S N O O N S O N O HN S Thiodicarb Methomyl Propazine, simazine and thiabendazole were not intentionally used to spike/treat the test material, but they were detected by the organisers at concentrations below 1 ppb due to impurities of the commercial formulations.
Sample 17 SM5 Propazine (Q-TOF) C ~ 1.3 ppb 1ppb Standard Potato Propazine [M+H] + : 23.1167 C 9 H 16 ClN 5 Therbuthylazine MS Spectra - Sample 17 SM5 MS Spectra - 1ppb Propazine Potato
Propazine (LC-QQQ) Standard 1ppb Potato SRM1: 23 / 146 Standard 1ppb Potato Ratio SRM2/SRM1: 3% SRM2: 23 / 188 Sample 1 SM5 SRM1: 23 / 146 C ~ 1.5 ppb Sample 1 SM5 Ratio SRM2/SRM1: 29% SRM2: 23 / 188
Simazine (Q-TOF) 2ppb Standard Potato Simazine [M+H] + : 22.853 C 7 H 12 ClN 5 Sample 17 SM5 C ~ 2.4 ppb MS Spectra - 2ppb Simazine Potato MS Spectra - Sample 17 SM5
Standard 1ppb Potato Almería 23 rd -25 th October 213 SRM2: 22 / 14 Simazine (LC-QQQ) Standard 1ppb Potato SRM3: 22 / 124 Ratio SRM2/SRM1: 57% Ratio SRM3/SRM1: 53% Ratio SRM3/SRM2: 94% Standard 1ppb Potato SRM1: 22 / 132 Sample 1 SM5 SRM2: 22 / 14 C ~ 2.3 ppb Sample 1 SM5 Sample 1 SM5 SRM3: 22 / 124 SRM1: 22 / 132 Ratio SRM2/SRM1: 63% Ratio SRM3/SRM1: 55% Ratio SRM3/SRM2: 88%
x1 5 2.6 x1 2.4 2.2 2 1.8 1.6 1.4 1.2 1.8.6.4.2 5 5.5 5 4.5 4 3.5 3 2.5 2 1.5 1.5 Almería 23 rd -25 th October 213 +ESI EIC(22.433) Scan Frag=9.V 17A_SM5.d Sample 17 SM5 +ESI EIC(22.433) Scan Frag=9.V 1ppb_SAS_Potato.d 1 ppb Thiabendazole Thiabendazole (Q-TOF) Thiabendazole [M+H] + : 22.433 C 1 H 7 N 3 S 3.6 3.65 3.7 3.75 3.8 3.85 3.9 3.95 4 4.5 4.1 4.15 4.2 4.25 4.3 4.35 4.4 4.45 4.5 4.55 4.6 4.65 4.7 4.75 4.8 4.85 4.9 Counts vs. Acquisition Time (min) 5 x1 2.5 2 1.5 +ESI Scan (4.76 min) Frag=9.V 17A_SM5.d MS Spectra - Sample 17 SM5 125.9863 No formula match 22.186 ([C11 H23 N O2]+H)+ 1.5 5 x1 5 4 12.341 +ESI Scan (4.143 min) Frag=9.V 1ppb_SAS_Potato.d 167.127 121.59 13.1588 141.958 158.3 182.9853 11.168 151.358 172.944 194.118 214.9172 223.638 MS Spectra - 1ppb Thiabendazole Potato 22.434 ([C1 H7 N3 S]+H)+ 3 2 1 125.9863 12.341 121.59 167.132 13.1591 141.9586 158.33 11.164 151.357 182.9848 173.298 194.1176 214.9171 223.687 9 95 1 15 11 115 12 125 13 135 14 145 15 155 16 165 17 175 18 185 19 195 2 25 21 215 22 225 23 Counts vs. Mass-to-Charge (m/z)
Thiabendazole (LC-QQQ) Standard 1ppb Potato SRM2: 22 / 131 Standard 1ppb Potato Ratio SRM2/SRM1: 93% SRM1: 22 / 175 Sample 1 SM5 SRM2: 22 / 131 C ~.9 ppb Sample 1 SM5 Ratio SRM2/SRM1: 95% SRM1: 22 / 175
22 Evaluated Pesticides (21 added ) 1 Degradation product # (in green pesticides with concentration <1 ppb) 22 Pesticides= 2+5+15 Aldicarb sulfone Aldicarb sulfoxide Atrazine Beta-Cyfluthrin Bromoxynil Clomazone Dieldrin Diuron Fluazinam Flufenacet Metamitron Methomyl# Metribuzin Molinate Oxamyl Picloram Picolinafen Propamocarb Prosulfocarb Quinoclamine Thiodicarb# Triflumizole Total Number of Reported Pesticides 5 5 53 51 4 49 53 46 31 45 39 5 51 37 52 1 39 47 46 22 5 42 % of Reported Pesticides 85 85 9 86 68 83 9 78 53 76 66 85 86 63 88 17 66 8 78 37 85 71
45 46 46 47 49 5 5 5 5 51 51 52 53 53 * 39 39 4 42 37 31 22 1 Dieldrin Atrazine Oxamyl Metribuzin Beta Cyfluthrin Thiodicarb Methomyl (not spiked) Aldicarb sulfoxide Aldicarb sulfone Clomazone Propamocarb Prosulfocarb Diuron Flufenacet Triflumizole Bromoxynil Picolinafen Metamitron Molinate Fluazinam Quinoclamine Picloram 6 5 4 3 2 1 SM5 No of Reported Pesticides (57 Laboratories Reported Data) * * * * * * * * * * Concentration lower than.1 mg/kg No of Reports
93 93 Dieldrin Atrazine Almería 23 rd -25 th October 213 SM5 % of Reported Data by Pesticide (57 Laboratories Reported Data) 91 * 89 89 88 * * * 88 88 88 86 82 * 81 81 79 74 * 7 68 68 65 54 39 18 Oxamyl Metribuzin Beta-Cyfluthrin Thiodicarb Methomyl (not spiked) Aldicarb sulfoxide Aldicarb sulfone Clomazone Propamocarb Prosulfocarb Diuron Flufenacet Triflumizole Bromoxynil Picolinafen Metamitron Molinate Fluazinam Quinoclamine Picloram 1 9 8 7 6 5 4 3 2 1 * * * * * Concentration lower than.1 mg/kg % of Reports
Fv15 % of Reported Data by Pesticide 1 9 8 7 6 5 4 3 % of Reports 2 1 Fluopicolide Flutolanil Fosthiazate Spirodiclofen Pencycuron Acephate Iprovalicarb Linuron Methiocarb Chlorpropham Chlorothalonil Prochloraz Thiabendazole Cypermethrin Procymidone Azoxystrobin Diazinon Preliminary Results
% of Reported Data by Laboratory (*NRL) (21+1 Pesticides Included) 9% 65% 24% 1 1 1 1 95 95 95 95 95 95 95 95 95 95 91 91 91 91 86 86 86 86 86 86 86 86 86 82 82 82 82 82 82 77 77 73 73 73 68 68 68 68 68 64 64 59 59 55 55 55 5 5 41 32 23 18 9 Lab53 Lab42 Lab33* Lab2 Lab58* Lab56 Lab43 Lab41 Lab39 Lab38 Lab34* Lab3 Lab11 Lab5* Lab46* Lab26 Lab17 Lab13 Lab59 Lab49 Lab47 Lab37 Lab35 Lab29 Lab24* Lab16* Lab14* Lab57 Lab55* Lab23 Lab21 Lab2* Lab1 Lab44 Lab18 Lab4 Lab8 Lab4* Lab31 Lab22 Lab1* Lab9 Lab6* Lab19 Lab7 Lab61 Lab12* Lab54 Lab48 Lab25* Lab36 Lab15* Lab6 Lab5 Lab51 Lab28 Lab32 Lab3* 12 1 8 6 4 2 % of Reported Pesticides
1 9 8 7 6 5 4 9 92 92 9 76 73 6 65 3 2 2 2 22 24 1 SM2 SM3 SM4 SM5 % laboratories with more than 5% of pesticides reported % laboratories with more than 7% of pesticides reported % laboratories with more than9% of pesticides reported
Other reported pesticides The test material was spiked/treated with thiodicarb, which degrades to methomyl. The test material was not spiked/treated with methomyl. Propazine, simazine and thiabendazole were not intentionally used to spike/treat the test material, but they were detected by the organisers at concentrations below 1 ppb due to impurities of the commercial formulations. Ethoxyquin has been reported by 3 laboratories but after the analysis by the organiser, it was not detected in the sample, all the other reported pesticides were detected only by one or two laboratories only. Ethoxyquin
Sample 17 SM5 Ethoxyquin (Q-TOF) 1ppb Ethoxyquin Potato Ethoxyquin [M+H] + : 218.1539 C 14 H 19 NO MS Spectra - 1ppb Ethoxyquin Potato R t : 8.1 min MS Spectra - Sample 17 SM5 R t : 8.64 min No formula match
Ethoxyquin (LC-QQQ) Standard 1ppb Potato SRM2: 218 / 16 Standard 1ppb Potato Ratio SRM2/SRM1: 1% SRM1: 218 / 174 Sample 1 SM5 Ratio SRM2/SRM1: 11% SRM2: 218 / 16 Sample 1 SM5 SRM1: 218 / 174
5 53 56 55 52 54 48 48 51 54 57 49 49 51 45 42 41 4 41 32 24 22 19 16 11 11 11 12 13 1 1 1 11 11 1 13 1 11 9 9 8 8 8 8 8 7 7 7 7 5 5 4 3 3 3 2 2 1 1 1 Triflumizole Thiodicarb Quinoclamine Prosulfocarb Propamocarb Picolinafen Picloram Oxamyl Molinate Metribuzin Methomyl* Metamitron Flufenacet Fluazinam Diuron Dieldrin Clomazone Bromoxynil Beta-Cyfluthrin Atrazine Aldicarb sulfoxide Aldicarb sulfone 7 6 5 4 3 2 1 SM-5 Techniques (Full Scan) *not spiked Total Number of Reported Detections (some laboratories apply more than one technique) Full Scan GC Full Scan LC
Full Scan Full Scan Full Scan
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