EU proficiency test on Cereals CRL for Cereals and Feedingstuff EU-PTC2 (part 1)

Transcription

1 EU proficiency test on Cereals CRL for Cereals and Feedingstuff EU-PTC2 (part 1) Mette Erecius Poulsen, Susan Strange Herrmann, Karen Hjort, Hanne Bjerre Christensen Copenhagen, 18 September 2008

2 2 Calendar Activity Sample Treatment, milling, homogenisation and storage. Homogeneity and stability tests. Invitation to laboratories to participate, including Calendar, Pesticide List, instructions on how to register, and link to website for further information e.g. Protocol and how to report results and methods used Dates September January 2008 November 2007 Deadline for receiving Application Form from invited laboratories. 20 January 2008 Test material distribution. 18 February 2008 Deadline for receipt of results on the online submission website 16 March 2008 Preliminary Report May 2008 Final Report October 2008

3 3 Participation Austria * 4 Latvia * 1 Belgium * 3 Lithuania * 1 Bulgaria * 1 Luxembourg * 1 Cyprus * 1 Norway 1 Czech Republic ** 3 Poland ** 7 Denmark * 2 Portugal * 3 Estonia * 1 Romania ** 2 Finland * 1 Slovakia * 1 France * 2 Slovenia ** 3 Germany * 9 Spain ** 4 Greece ** 3 Sweden * 2 Hungary * 2 The Netherlands ** 2 Ireland * 1 UK * 1 Italy * 10 Total 27 countries 72

4 4 Participation NRLs 74 laboratories registered representing 27 countries and 26 Member States 72 laboratories submitted results 33 of these were NRL representing 26 Member state Assosiates Norway

5 5 PT-C2 Possible pesticide list *Alpha-cypermethrin *Azoxystrobin *Bifenthrin Carbaryl *Carbendazim Chlormequat (expressed as cation) Chlorothanlonil *Chlorpyrifos *Chlorpyrifos-methyl *Cypermethrin *Cyproconazole *Deltamethrin Diazinon *Difenoconazole *Endosulfan (α + ß + Sulphate expressed as Endosulfan) Endosulfan α Endosulfan β Endosulfan sulphate *Epoxiconazole Fenhexamid *Fenpropimorph Fluquinconazole Glyphosate *Imazalil *Iprodione *Kresoxim-methyl *Lambda-cyhalothrin *Lindane (gamma-hch) *Malathion (Malathion + Malaoxon,expressed as Malathion) Malathion Malaoxon Mepiquat (expressed as cation) Metconazole *Methacrifos *Methomyl (Methomyl + Thiodicarb,expressed as Methomyl) Methomyl Thiodicarb *Parathion (only parent compound) *Penconazole *Permethrin *Pirimicarb *Pirimiphos-methyl *Prochloraz (only parent compound) *Procymidone *Propiconazole Spiroxamine *Tebuconazole *Thiabendazole *Thiophanate-methyl Triadimefon (Triadimefon + Triadimenol express. as Triadimefon) Triadimefon Triadimenol

6 6 Field treatment of wheat incurred pesticides Faculty of Agricultural Sciences, University of Aarhuss Active substance Application time Produkt Dose MRL Target conc. mg/kg Residue Chlormequat days before harvest Cycocel g as/ha Alpha-cypermethrin days before harvest Fastac g as/ha Bifentrin days before harvest 500 as/ha Carbendazim days before harvest Bavistin DF 2000 as/ha Difenconazole days before harvest Score 500g as/ha 0.02 (barley) Epoxiconazole days before harvest Opus 1000 as/ha Iprodione days before harvest Rovral 1000 as/ha Pirimicarb days before harvest Pirimor G 2500 as/ha Prochloraz days before harvest Sportak as/ha Spiroxamin days before harvest Impulse 2500 as/ha Trifloxystrobin days before harvest Flint 2500 as/ha Chlorpyrifos-methyl 3-5 days before harvest Reldan g as/ha Glyphosate 3-5 days before harvest Roundup 3000 as/ha Malathion 3-5 days before harvest 1500 as/ha

7 7

8 8 Spiking of wheat 4 times 1 kg wheat were spike with 4 different pesticides Active substance Produkt MRL Target conc. mg/kg Residue Difenconazole Score Malathion Prochloraz Sportak Azoxystrobin Amistar The spiked wheat was mixed with 56 kg of wheat with incurred pesticides

9 Spike procedure 9

10 Homogeniety 10 Azoxystrobin Alfa-cypermethrin Bifenthrin Carbendazim Chlropyriphosmethyl Chlormequat Difenconazole Epoxyconazole Mean (mg/kg) Ss/σ Pass/Fail Pass Pass Pass Pass Pass Pass Pass Pass Glyphosate Iprodion Malathion Pirimicarb Prochloraz Spiroxamine Trifloxystrobin Mean (mg/kg) Ss/σ Pass/Fail Pass Pass Pass Pass Pass Pass Pass

11 Stability 11 Azoxystrobin Alfa-cypermethrin Bifenthrin Carbendazim Chlorpyriphosmethyl Chlormequat Difenconazole Epoxyconazole Day 1 (mean) Day 2 (mean) % 1% 4% 3% 1% 3% 8% 0% 1% Glyphosate Iprodion Malathion Pirimicarb Prochloraz Spiroxamine Trifloxystrobin Day 1 (mean) Day 2 (mean) % 4% 7% 3% 3% 2% 3% 2%

12 12 Sample shipment Fedex Samples were distributed on Monday 18 February Most samples were delivered on 19 or 20 February All samples were delivered before 22 February

13 13 Result submission

14 14 Result submission

15 Result submission 15

16 16 Results overview No. of reported results No. of NA False negatives % results Azoxystrobin Alpha-cypermethrin Cypermethrin Cypermethrin all Bifentrin Carbendazim Chlormequat Chlorpyrifos-methyl Difenconazole Epoxiconazole Glyphosate Iprodione Malathion Pirimicarb * 60 Prochloraz Spiroxamin * 71 Trifloxystrobin

17 17 Results cypermethrin/alpha-cypermethrin No. of reported results No. of NA False negatives % results Azoxystrobin Alpha-cypermethrin Cypermethrin Cypermethrin all Bifentrin Carbendazim Chlormequat Chlorpyrifos-methyl Difenconazole Epoxiconazole Glyphosate Iprodione Malathion Pirimicarb * 60 Prochloraz Spiroxamin * 71 Trifloxystrobin

18 18 Results high number of NA No. of reported results No. of NA False negatives % results Azoxystrobin Alpha-cypermethrin Cypermethrin Cypermethrin all Bifentrin Carbendazim Chlormequat Chlorpyrifos-methyl Difenconazole Epoxiconazole Glyphosate Iprodione Malathion Pirimicarb * 60 Prochloraz Spiroxamin * 71 Trifloxystrobin

19 19 Results low number of reported result and low assigned value No. of reported results No. of NA False negatives % results Azoxystrobin Alpha-cypermethrin Cypermethrin Cypermethrin all Bifentrin Carbendazim Chlormequat Chlorpyrifos-methyl Difenconazole Epoxiconazole Glyphosate Iprodione Malathion Pirimicarb * 60 Prochloraz Spiroxamin * 71 Trifloxystrobin

20 FFP (25%) versus Qn all result FFP Qn 20 Azoxystrobin Cypermethrin Bifentrin Carbendazim Chlormequat Alphacypermethrin Chlorpyrifosmethyl Difenconazole Epoxiconazole Iprodione Malathion Pirimicarb Prochloraz Spiroxamin Trifloxystrobin

21 FFP (25%) versus Qn water FFP Qn Qn -water 21 Azoxystrobin Cypermethrin Bifentrin Carbendazim Chlormequat Alphacypermethrin Chlorpyrifosmethyl Difenconazole Epoxiconazole Iprodione Malathion Pirimicarb Prochloraz Spiroxamin Trifloxystrobin

22 22 Distributions Azoxystrobin < >0.4 Concentration Frecuency Alpha-cypermethrin < >0.5 Concentration Frecuency Cypermethrin < >0.5 Concentration Frecuency Bifenthrin < >0.13 Concentration Frecuency Carbendazim >0.8 Concentration Frecuency Chlormequat < >0.3 Concentration Frecuency

23 23 Distributions Chlorpyrifos-methyl < Concentration Frecuency Difenoconazole < >3.0 Concentration Frecuency Epoxiconazole < >0.25 Concentration Frecuency Iprodione < Concentration Frecuency Malathion < >0.2 Concentration Frecuency Pirimicarb < >0.08 Concentration Frecuency Prochloraz < >0.4 Concentration Frecuency Spiroxamin < >0.25 Concentration Frecuency Trifloxostrobin < >0.6 Concentration Frecuency

24 24 False positives Lab no. MRRL Reported results Reporting limit from lab False positive ptc213 Vinclozolin no malaoxon no ptc210 Lindane no Endosulfane no Endosulfane- alpha no Diazinon no Chlorpyrifos no ptc237 Fenhexamid yes ptc238 Fenhexamid yes

25 25 False negatives No. of false Negatives MRRL Assigned Value Resulting z- score Azoxystrobin Bifentrin (Alpha-)cypermethrin Carbendazim Chlormequat Chlorpyrifos-methyl Difenconazole Epoxiconazole Iprodione Malathion Pirimicarb Prochloraz Spiroxamin Trifloxystrobin

26 or 1: LC or 2: GC or 3: not specificed or both Azoxystrobin LC/GC Acceptable Questionable Unacceptable Number of labs 91% 9% 0% 64 Assigned value: mg/kg z-scores

27 or 1: LC or 2: GC or 3: not specificed or both Alpha-cypermethrin LC/GC Acceptable Questionable Unacceptable Number of labs 87% 7% 7% 46 Assigned value: mg/kg 2 2 * * * * false negatives z-scores

28 or 1: LC or 2: GC or 3: not specified or both Cypermethrin LC/GC Acceptable Questionable Unacceptable Number of labs 66% 16% 19% Assigned value: mg/kg z-scores * * * false negatives

29 or 1: LC or 2: GC or 3: not specified or both Bifenthrin LC/GC Acceptable Questionable Unacceptable Number of labs 91% 8% 2% 65 Assigned value: mg/kg * * false negative z-scores

30 or 1: LC or 2: GC or 3: not specified or both Carbendazim LC/GC Acceptable Questionable Unacceptable Number of labs 78% 16% 6% 49 Assigned value: mg/kg * * * false negative z-scores

31 or 1: LC or 2: GC or 3: not specified or both Chlormequat LC/GC Acceptable Questionable Unacceptable Number of labs 92% 8% 0% Assigned value: mg/kg z-scores

32 or 1: LC or 2: GC or 3: not specified or both Chlorpyrifos-methyl Acceptable Questionable Unacceptable Number of labs 66% 33% 1% 70 Assigned value: mg/kg * * false negative z-scores

33 or 1: LC or 2: GC or 3: not specified or both Chlorpyrifos-methyl LC/GC Acceptable Questionable Unacceptable Number of labs 66% 33% 1% 70 Assigned value: mg/kg * * false negative z-scores

34 or 1: LC or 2: GC or 3: not specified or both Difenconazole LC/GC Acceptable Questionable Unacceptable Number of labs 86% 10% 4% 49 Assigned value: mg/kg * * false negative z-scores

35 or 1: LC or 2: GC or 3: not specified or both Epoxiconazole LC/GC Acceptable Questionable Unacceptable Number of labs 83% 4% 6% 48 Assigned value: mg/kg *** * false negative z-scores

36 or 1: LC or 2: GC or 3: not specified or both Iprodione LC/GC Acceptable Questionable Unacceptable Number of labs 61% 31% 8% 59 Assigned value: mg/kg 2 1 * * false negative z-scores

37 or 1: LC or 2: GC or 3: not specified or both Malation Acceptable Questionable Unacceptable Number of labs 79% 13% 4% 67 Assigned value: mg/kg ** * false negative z-scores

38 or 1: LC or 2: GC or 3: not specified or both Pirimicarb LC/GC Acceptable Questionable Unacceptable Number of labs 65% 2% 2% 63 Assigned value: mg/kg ******************** * false negative z-scores

39 or 1: LC or 2: GC or 3: not specified or both Procloraz LC/GC Acceptable Questionable Unacceptable Number of labs 86% 9% 5% 57 Assigned value: mg/kg *** * false negative z-scores

40 or 1: LC or 2: GC or 3: not specified or both Spiroxamin LC/GC Acceptable Questionable Unacceptable Number of labs 68% 15% 13% 53 Assigned value: mg/kg ** * false negative z-scores

41 or 1: LC or 2: GC or 3: not specified or both Trifloxystrobin LC/GC Acceptable Questionable Unacceptable Number of labs 97% 3% 0% 61 Assigned value: mg/kg z-scores

42 42 Glyphosate Lab mg/kg

43 43 Results - Overview No. of reported results False negatives Acceptable Questionable Unacceptable Azoxystrobin Alpha-cypermethrin Cypermethrin Cypermethrin all Bifentrin Carbendazim Chlormequat Chlorpyrifos-methyl Difenconazole Epoxiconazole Glyphosate 5 5 Iprodione Malathion Pirimicarb Prochloraz Spiroxamin Trifloxystrobin

44 44 Results - > 90% acceptable No. of reported results False negatives Acceptable Questionable Unacceptable Azoxystrobin Alpha-cypermethrin Cypermethrin Cypermethrin all Bifentrin Carbendazim Chlormequat Chlorpyrifos-methyl Difenconazole Epoxiconazole Glyphosate 5 5 Iprodione Malathion Pirimicarb Prochloraz Spiroxamin Trifloxystrobin

45 45 Results 80-90% acceptable No. of reported results False negatives Acceptable Questionable Unacceptable Azoxystrobin Alpha-cypermethrin Cypermethrin Cypermethrin all Bifentrin Carbendazim Chlormequat Chlorpyrifos-methyl Difenconazole Epoxiconazole Glyphosate 5 5 Iprodione Malathion Pirimicarb Prochloraz Spiroxamin Trifloxystrobin

46 46 Results - <80% acceptables No. of reported results False negatives Acceptable Questionable Unacceptable Azoxystrobin Alpha-cypermethrin Cypermethrin Cypermethrin all Bifentrin Carbendazim Chlormequat Chlorpyrifos-methyl Difenconazole Epoxiconazole Glyphosate 5 5 Iprodione Malathion Pirimicarb Prochloraz Spiroxamin Trifloxystrobin

47 47 Catagory A and B Acceptable 70 % Questionable 9 % Unacceptable 21 % % 39% 0 Category A Category B

48 48 Weighted z-scores *274 *216 * *225 *242 *260 * *255 *219 *234 * * * *214 *206 * *245 *253 * * * *229 Weighted Summed z-scores OFL NRL