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

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Stewart Baldwin
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Calendar ACTIVITY DATE Sending Application Form to laboratories 9th May 2013 Sending calendar and pesticides target list to participant laboratories.

2 Calendar ACTIVITY DATE Sending Application Form to laboratories 9th May 2013 Sending calendar and pesticides target list to participant laboratories. 14th May 2013 Deadline for receiving Application Form from laboratories. 17th May 2013 Sample distribution. 10th June 2013 Deadline for receiving results 28th June 2013 Preliminary Report: only results, no statistical treatment. July 2013 Final Report October 2013

3 Participants EU and EFTA countries 1 Austria 4 Belgium 1 Denmark 1 Finland 3 France 8 Germany 2 Hungary 1 Ireland 8 Italy 1 Norway* 1 Poland 1 Romania 1 Slovakia 8 Spain 1 Sweden 2 Switzerland* 2 The Netherland *EFTA countries Non EU and EFTA countries 1 China 1 Egypt 1 Israel 1 Saudi Arabia 1 Serbia 1 Uruguay 52 laboratories in total (16 of them NRLs)

4 Incurred Compounds 20 LC a - and GC b - amenable pesticides 15 pesticides evaluated Acetamiprid Buprofezin Carbendazim Chlorpyrifos Cypermethrin Difenoconazole Endosulfan beta Ethofenprox Fenpropathrin Imidacloprid Lambda cyhalothrin Methomyl Parathion ethyl Pyridaben Tebuconazole Not evaluated (Median < 4MRRL) Bifenthrin Endosulfan alpha Endosulfan sulphate Omethoate Not evaluated (Homogeneity test fails) Thiophanate methyl

5 Preparation of the test item Real sample Milling Homogenation Extend the tea on the crystallizer Samples distribution Sample packing Sieving

6 Homogeneity Pesticides Homogeneity median concentration (mg/kg) Assigned value (mg/kg) Acetamiprid Buprofezin Carbendazim Chlorpyrifos Cypermethrin Difenoconazole Endosulfan beta Ethofenprox Fenpropathrin Imidacloprid Lambda cyhalothrin Methomyl Parathion ethyl Pyridaben Tebuconazole Thiophanate methyl* *Homogeneity test fails

7 Almería 23rd-25th October 2013 Results

8 Sumary of reported results Pesticides No. of Reported Results No. of False Negative Results No. of Not Analysed Results Percentage of Reported Results (out of 46)* Acetamiprid Bifenthrin* Buprofezin Carbendazim Chlorpyrifos Cypermethrin Difenoconazole Endosulfan alpha* Endosulfan beta Endosulfan sulfate* Ethofenprox Fenpropathrin Imidacloprid Lambda cyhalothrin Methomyl Omethoate* Parathion ethyl Pyridaben Tebuconazole Thiophanate methyl** *Median < 4 MRRL **Homogeneity test fails

9 False positives Laboratory Code Pesticide Concentration (mg/kg) Determination Technique RL (mg/kg) MRRL (mg/kg) Extraction method used Lab007 Orthophenylphenol LC-MS/MS (QQQ) QuEChERS Lab009 Penconazole LC-MS/MS (QQQ) Modified QuEChERS with CaCl 2 Lab011 Amitraz LC-MS/MS (QQQ) Modified QuEChERS with CaCl 2 Lab012 Methidathion GC-MS/MS (QQQ) L-L extraction Lab013 Carbaryl Other Modified QuEChERS with CaCl 2 Lab034 Folpet GC-MS/MS (QQQ), FPD, ECD miniluke Ethoprophos LC and GC MS/MS (QQQ) QuEChERS Lab043 Ethoprophos LC-MS/MS (QQQ) QuEChERS Lab043 Triazophos LC-MS/MS (QQQ) QuEChERS

10 False negatives Laboratory Code Acetamiprid Buprofezin Chlorpyrifos Cypermethrin (cypermethrin incl. other mixtures of constituent isomers (sum of isomers)) Difenoconazole Endosulfan beta Etofenprox Fenpropathrin Imidacloprid Methomyl Parathion-ethyl Pyridaben Tebuconazole Thiophanatemethyl Lab003 ND ND ND Lab007 ND ND ND Lab010 ND Lab011 ND ND Lab013 ND Lab016 ND ND ND ND ND ND Lab022 ND ND ND Lab025 ND ND ND Lab027 ND ND ND ND ND Lab034 ND ND ND ND Lab043 ND ND ND ND ND Lab051 ND ND ND Lab054 ND ND ND ND QuEChERS CaCl 2 EtAc MiniLuke MeOH Other False negatives (%) over the total number of results per extraction method QuEChERS: 6.9% CaCl 2 : 6.3% Ethyl Acetate method: 2.3% MeOH extraction: 6.7% miniluke: 6.1% Other methods: 2.2%

11 Tea matrix compounds. QuEChERs_CaCl2 extraction method. Dilution:5 LC-TOF-MS Absolute height counts Green tea 3879 compounds PT01_Green tea 6659 compounds

12 Median values, uncertainty and %RSDs for all pesticides present in the test item Pesticides MRRL (mg/kg) Median (mg/kg) u (mg/kg) FFP RSD (%) Qn RSD (%) Acetamiprid Buprofezin Carbendazim Chlorpyrifos Cypermethrin Difenoconazole Endosulfan beta Ethofenprox Fenpropathrin Imidacloprid Lambda cyhalothrin Methomyl Parathion ethyl Pyridaben Tebuconazole

13 Lab003 Lab027 Lab051 Lab016 Lab054 Lab011 Lab041 Lab034 Lab012 Lab007 Lab043 Lab015 Lab025 Lab009 Lab019 Lab014 Z-Scores Acetamiprid 72.5% Acceptable 5.0% Questionable 22.5% Unacceptable Median: mg/kg Q Et * * * * *False Negatives No water addition

14 Lab010 Lab034 Lab051 Lab007 Lab054 Lab003 Lab016 Lab036 Lab041 Lab011 Lab014 Lab025 Lab027 Lab013 Lab015 Lab043 Lab019 Lab009 Lab042 Lab012 Z-Scores Buprofezin 79.6% Acceptable 6.8% Questionable 13.6% Unacceptable Median: mg/kg Q ml * * * *False Negatives No water addition

15 Lab016 Lab043 Lab051 Lab010 Lab027 Lab022 Lab003 Lab011 Lab015 Lab041 Lab007 Lab054 Lab034 Lab025 Lab012 Lab009 Lab014 Lab019 Z-Scores Carbendazim 57.1% Acceptable 23.8% Questionable 19.1% Unacceptable Median: mg/kg O C ml No water addition

16 Lab013 Lab010 Lab022 Lab051 Lab016 Lab011 Lab054 Lab003 Lab041 Lab048 Lab036 Lab042 Lab027 Lab007 Lab012 Lab025 Lab009 Lab034 Lab043 Lab015 Z-Scores Chlorpyrifos 88.6% Acceptable 4.6% Questionable 6.8% Unacceptable Median: mg/kg Q O ml * *False Negatives No water addition

17 Lab007 Lab016 Lab025 Lab043 Lab051 Lab054 Lab003 Lab036 Lab011 Lab034 Lab027 Lab013 Lab009 Z-Scores Cypermethrin 62.2% Acceptable 16.2% Questionable 21.6% Unacceptable Median: mg/kg ml Q * * * * * * ***** *False Negatives No water addition

18 Lab051 Lab054 Lab011 Lab007 Lab010 Lab025 Lab027 Lab036 Lab034 Lab016 Lab019 Lab041 Lab013 Lab009 Lab015 Lab012 Lab043 Z-Scores Difenoconazole 90.2% Acceptable 4.9% Questionable 4.9% Unacceptable Median: mg/kg Q ml ml * *False Negatives

19 Lab043 Lab051 Lab016 Lab007 Lab054 Lab003 Lab022 Lab012 Lab036 Lab011 Lab042 Lab027 Lab034 Lab013 Lab009 Lab025 Lab015 Z-Scores Endosulfan beta 70.7% Acceptable 22.0% Questionable 7.3% Unacceptable Median: mg/kg Q Q * * * ** *False Negatives No water addition

20 Lab043 Lab051 Lab015 Lab025 Lab048 Lab036 Lab054 Lab034 Lab011 Lab027 Lab019 Lab007 Lab012 Lab009 Z-Scores Etofenprox 81.6% Acceptable 7.9% Questionable 10.5% Unacceptable Median: mg/kg C Q C * * ** *False Negatives No water addition

21 Lab034 Lab051 Lab016 Lab054 Lab036 Lab048 Lab011 Lab015 Lab013 Lab019 Lab043 Lab007 Lab027 Lab012 Lab009 Lab025 Lab042 Z-Scores Fenpropathrin 90.3% Acceptable 2.4% Questionable 7.3% Unacceptable Median: mg/kg Q Q Et * *False Negatives No water addition

22 Lab003 Lab016 Lab027 Lab051 Lab011 Lab054 Lab007 Lab014 Lab043 Lab012 Lab025 Lab041 Lab015 Lab034 Lab009 Lab019 Z-Scores Imidacloprid 72.5% Acceptable 15.0% Questionable 12.5% Unacceptable Median: mg/kg * ** * * * * *False Negatives No water addition

23 Lab016 Lab051 Lab012 Lab036 Lab025 Lab003 Lab022 Lab042 Lab011 Lab010 Lab048 Lab054 Lab015 Lab034 Lab007 Lab013 Lab027 Lab019 Lab009 Lab043 Z-Scores Lambda cyhalothrin 86.4% Acceptable 9.1% Questionable 4.5% Unacceptable Median: mg/kg O O mlc Q No water addition

24 Lab027 Lab003 Lab007 Lab016 Lab051 Lab011 Lab025 Lab054 Lab043 Lab015 Lab012 Lab009 Lab034 Lab041 Z-Scores Methomyl 65.8% Acceptable 5.3% Questionable 28.9% Unacceptable Median: mg/kg ml Q * * * * * * * * * *** *False Negatives No water addition

25 Lab027 Lab022 Lab051 Lab054 Lab003 Lab016 Lab011 Lab007 Lab036 Lab025 Lab034 Lab019 Lab009 Lab043 Lab042 Lab015 Lab013 Lab048 Z-Scores Parathion-ethyl 81.0% Acceptable 14.2% Questionable 4.8% Unacceptable Median: mg/kg * * *False Negatives No water addition

26 Lab022 Lab051 Lab016 Lab003 Lab048 Lab010 Lab036 Lab054 Lab011 Lab041 Lab014 Lab019 Lab015 Lab027 Lab034 Lab012 Lab009 Lab043 Lab025 Lab013 Lab042 Z-Scores Pyridaben 84.4% Acceptable 6.7% Questionable 8.9% Unacceptable Median: mg/kg O M ml Q * *False Negatives No water addition

27 Lab051 Lab022 Lab054 Lab036 Lab011 Lab012 Lab025 Lab027 Lab007 Lab010 Lab016 Lab041 Lab034 Lab015 Lab019 Lab013 Lab009 Lab043 Lab042 Z-Scores Tebuconazole 88.4% Acceptable 2.3% Questionable 9.3% Unacceptable Median: mg/kg C Q * *False Negatives No water addition

28 Classification of Z-scores for the pesticides reported Pesticides Acceptable (%) Questionable (%) Unacceptable (%) Acetamiprid Buprofezin Carbendazim Chlorpyrifos Cypermethrin Difenoconazole Endosulfan beta Ethofenprox Fenpropathrin Imidacloprid Lambda cyhalothrin Methomyl Parathion ethyl Pyridaben Tebuconazole

29 Category A and B 24 Laboratories Reported 90% analytes (14 pesticides) Without false positives 48% Cat A 52% Cat B 22 Laboratories Reported < 90% analytes (14 pesticides) and/or false positives 2 laboratories reported one false positive with 90% analytes

30 Almería 23rd-25th October 2013 Special case

31 5,0 4,0 3,0 2,0 1,0 0,0-1,0-2,0-3,0-4,0-5,0 Lab016 Lab043 Lab051 Lab010 Lab027 Lab022 Lab003 Lab011 Lab015 Lab041 Lab007 Lab054 Lab034 Lab025 Lab012 Lab009 Lab014 Lab019 Carbendazim 57.1% Acceptable 23.8% Questionable 19.1% Unacceptable Median: mg/kg O C ml No water addition

32 5,0 4,0 3,0 2,0 1,0 0,0-1,0-2,0-3,0-4,0-5,0 Lab007 Lab027 Lab054 Lab016 Lab025 Lab011 Lab014 Lab009 Lab019 Lab012 Lab034 Lab015 Lab043 Thiophanate methyl 59.5% Acceptable 5.4% Questionable 35.1% Unacceptable Median: mg/kg Q Q Q * * *False Negatives No water addition

33 5,0 4,0 3,0 2,0 1,0 0,0 1,0 2,0 3,0 4,0 5,0 Carbendazim + Thiophanate methyl expressed as Carbendazim 78.4% Acceptable 8.1% Questionable 13.5% Unacceptable Median: mg/kg Q C No water addition Lab027 Lab016 Lab011 Lab007 Lab054 Lab025 Lab009 Lab015 Lab014 Lab034 Lab012 Lab019 Lab043

34 Qn (%) Qn (%) Carbendazim Thiophanate methyl Carb + TFM sum

35 5,0 4,5 4,0 Graph using individual values for Carbendazim and Thiophanate methyl EUPT-PT01 Graphical representation for laboratories in Category A 75.0% Acceptable 20.8% Questionable 4.2% Unacceptable 18 Laboratories 5 Laboratories 1 Laboratory 3,5 3,0 2,5 2,0 1,5 1,0 0,5 0,0 Lab015

36 Almería 23rd-25th October 2013 Conclusions

37 Conclusions Fifty-two laboratories participated in EUPT-T01 (Six from no EU or EFTA countries, 16 NRLs). Pesticides considered as positives were those which were reported by both the Organiser and the majority of participants. A higher dispersion (Qn) than in most fruits and vegetables have been observed (As maximum 44%). For carbendazim and thiophanate methyl, the results were influenced by the different degrees of degradation obtained by participants during the sample handling. QuEChERS without calcium chloride addition modificcation, presented a higher dispersion accounted as Qn than for the whole data reported (average Qn for QuEChERS was 41% whereas for the combined data, it was 34%). One compound did not pass the homogeneity test (thiophanate methyl). This fact is clearly as a consequence of some degradation to carbendazim. Overall, the results can be considered to be good with regard to the z-scores for each pesticide present in the test item, except for some pesticides which obtained a value more than 20% of unacceptable results (3 of them). It would appear that multiresidue methods such as QuEChERS have improved following modification (CaCl 2 addition). All of the laboratories applying the miniluke method obtained acceptable results in terms of z-scores, except for carbendazim.

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