Results of EUPT-CF10 Incurred and spiked pesticides in rye Mette Erecius Poulsen Holte, 20 September 2016 PTs on cereals/feed 2016 EUPT-CF10 Test material Rye flour Participants 178 (160) Compulsory target pesticides 134 Voluntary target pesticides 7 Incurred pesticides 10 Spiked pesticides 8 Total no. of pesticides 18 National Food Institute, Technical University of Denmark Advisory Group Quality Group Amadeo R. Fernández-Alba Antonio Valverde André de Kok Stewart Reynolds Antonio Valverde Magnus Jezussek Michelangelo Anastassiades Miguel Gamón Organising team at EURL Philippe Gros Mette Erecius Poulsen Ralf Lippold Susan Strange Herrmann Sonja Masselter Parvaneh Hajeb Stewart Reynolds Merete B. Ludwigsen Tuija Pihlström Lisbet Pilhkjær Finbarr Oregan Jens-Ole Frimann National Food Institute, Technical University of Denmark National Food Institute, Technical University of Denmark Activity Dates Announcement Calendar December 2015 Target Pesticide List EUPT-Registration Website 11 January 2016 Deadline for registration 1 February 2016 Release of Specific Protocol 29 February 2016 Distribution of Test items 7 March 2016 Deadline for Receipt and Acceptance of Test Materials within 24 hr on reciept 11 April 2016 Deadline for Result Submission at 13.00 CET Deadline for submission of additional method information for 15 April 2015 false negative results Preliminary Report (only compilation of results) 30 May 2015 Final Report December 2015 National Food Institute, Technical University of Denmark Target list - new pesticides and voluntary compounds • Acetamiprid From DIRECTIVE 2002/32/EC • Aldrin • Biphenyl • Voluntary: • Bromuconazole • Chlordane, cis- • Buprofezin • Chlordane, oxy • Chlorantraniliprole • Chlordane, trans- • Cymoxanil • Endrin • Dieldrin • Heptachlor • Famoxadone • Heptachlorepoxid-cis • Flutolanil • Heptachlorepoxid-trans • Methamidophos • Pencycuron • Propamocarb • Tau-Fluvalinate • Tefluthrin • Tetraconazole • Tetramethrin National Food Institute, Technical University of Denmark Acephate Difenoconazole Imidacloprid Prothioconazole-desthio Acetamiprid Diflubenzuron Iprodione Pyraclostrobin Aldrin Dimethoate Isocarbophos Pyrimethanil Azinphos-methyl Diniconazole Isoprothiolane Quinoxyfen Azoxystrobin Endosulfan-alpha Isoproturon Spiromesifen Bifenthrin Endosulfan-beta Kresoxim-methyl Spiroxamine Biphenyl Endosulfan-sulfate Lambda-cyhalothrin Tau-Fluvalinate Bixafen Epoxiconazole Lindane Tebuconazole Boscalid Ethion Linuron Tebufenozide Bromuconazole Ethirimol Malaoxon Tefluthrin Buprofezin Famoxadone Malathion Terbuthylazine Carbaryl Fenbuconazole Mandipropamid Tetraconazole Carbendazim Fenhexamid Metconazole Tetramethrin Carbofuran Fenitrothion Methacrifos Thiabendazole Carbofuran, 3-hydroxy Fenpropidin Methamidophos Thiacloprid Carboxin Fenpropimorph Methomyl Thiamethoxam Chlorantraniliprole Fenthion Metolachlor Thiodicarb Chlorfenvinphos Fenthion-oxon Metrafenone Thiophanate-methyl Chlorpropham (parent compound only) Fenthion-oxon-sulfone Metribuzin Triadimefon Chlorpyrifos Fenthion-oxon-sulfoxide Omethoate Triadimenol Chlorpyrifos-methyl Fenthion-sulfone Oxydemeton-methyl Triazophos Clothianidin Fenthion-sulfoxide Paclobutrazol Tricyclazole Cyfluthrin (sum of isomers) Fenvalerate and Esfenvalerate Parathion Trifloxystrobin Cymoxanil Fipronil (parent compound only) Penconazole Trifluralin Cypermethrin (sum of isomers) Flonicamid Pencycuron Triticonazole Cyproconazole Fludioxonil Pendimethalin Vinclozolin (parent compound only) Cyprodinil Fluopyram Permethrin (sum of isomers) DDD- p,p' Fluquinconazole Phenylphenol-ortho Voluntary DDE- p,p' Flusilazole Phosphamidon Chlordane, cis- DDT- o,p' Flutolanil Pirimicarb Chlordane, oxy DDT- p,p' Flutriafol Pirimicarb-desmethyl Chlordane, trans- Deltamethrin-cis Fluxapyroxad Pirimiphos-methyl Endrin Demeton-S-methylsulfone HCH-alpha Prochloraz (parent compound only) Heptachlor Diazinon HCH-beta Procymidone Heptachlorepoxid-cis Dichlorvos Hexaconazole Propamocarb Heptachlorepoxid-trans National Food Institute, Technical University of Denmark Dieldrin Imazalil Propiconazole Participation Country # labs Country # labs Country # labs Albania 1 France 8 Poland 16 Argentina 1 Germany 24 Portugal 2 Australia 1 Greece 3 Romania 9 Austria 2 Hungary 4 Serbia 2 Belgium 3 Iceland 1 Singapore 1 Brazil 3 India 2 Slovakia 2 Bulgaria 2 Indonesia 1 Slovenia 5 China 1 Ireland 1 Spain 22 Croatia 7 Israel 1 Sweden 2 Cyprus 2 Italy 25 Switzerland 1 Czech Republic 3 Latvia 1 Tanzania 2 Denmark 1 Lithuania 1 Thailand 3 Egypt 1 Luxembourg 1 United Kingdom 3 Estonia 1 Netherlands 6 Finland 2 Norway 2 Total 178 National Food Institute, Technical University of Denmark Participation Country # labs Country # labs Country # labs Albania 1 France 8 Poland 16 Argentina 1 Germany 24 Portugal 2 Australia 1 Greece 3 Romania 9 Austria 2 Hungary 4 Serbia 2 Belgium 3 Iceland 1 Singapore 1 Brazil 3 India 2 Slovakia 2 Bulgaria 2 Indonesia 1 Slovenia 3 China 1 Ireland 1 Spain 22 Croatia 7 Israel 1 Sweden 2 Cyprus 2 Italy 25 Switzerland 1 Czech Republic 3 Latvia 1 Tanzania 2 Denmark 1 Lithuania 1 Thailand 1 Egypt 1 Luxembourg 1 United Kingdom 3 Estonia 1 Netherlands 6 Finland 2 Norway 2 Total 178 National Food Institute, Technical University of Denmark Rye • Grown in Denmark in 2015 • Field treated by Aarhus University, Research Department Flakkebjerg National Food Institute, Technical University of Denmark Pesticides in test material Pesticide Field application Spike in laboratory Formulation or standard Azoxystrobin x Amistar Bixafen x Aviator Boscalid x Viverda Buprofezin x Analytical standard Carbendazim x Benlate Cypermethrin x x Cyperb Epoxiconazole x Viverda Fenpropidin x Tern Fluopyram x Propulse Isocarbophos x Analytical standard Metrafenone x Flexity Pencycuron x Analytical standard Pirimicarb-desmethyl x Analytical standard Prothioconazole x Aviator and Propulse Pyraclostrobin x Viverda Tebuconazole x Folicur Tetramethrin x Analytical standard Heptachlor x Analytical standard National Food Institute, Technical University of Denmark Spike procedure National Food Institute, Technical University of Denmark National Food Institute, Technical University of Denmark Sample shipment • Samples were distributed on Monday 7 and 8 March 2016 (17 February to non-EU and EFTA Countries) • Most samples were delivered to EU laboratories within one day National Food Institute, Technical University of Denmark Homogeniety test 2 2 Mean, mg/kg Ss c Ss < c Azoxys trobin 0.087 0.00000 0.0001 Pass Bixafen 0.073 0.00000 0.0001 Pass Boscalid 0.422 0.00030 0.0020 Pass Buprofezin 0.048 0.00000 0.0000 Pass Carbendazim 0.077 0.00000 0.0001 Pass Cypermethrin 0.140 0.00011 0.0004 Pass Epoxiconazole 0.173 0.00005 0.0004 Pass Fenpropidin 0.313 0.00007 0.0012 Pass Fluopyram 0.257 0.00006 0.0007 Pass Heptachlor 0.031 0.00000 0.0000 Pass Isocarbophos 0.048 0 0.0000 Pass Metribuzin 0.351 0.00057 0.0016 Pass Metrafenone 0.086 0.00001 0.0001 Pass Pencycuron 0.032 0.00000 0.0000 Pass Pirimicarb desmethyl 0.050 0 0.0000 Pass Prothioconazole desthio 0.112 0.00001 0.0002 Pass Pyraclostrobin 0.098 0.00002 0.0001 Pass Tebuconazole 0.099 0.00002 0.0001 Pass National Food Institute, Technical University of Denmark Stability test Storage at -18 degrees | x1 - yi | ≤ Mean, mg/kg | x1 - yi | 0.3×σ 0.3×σ Azoxys trobin 0.089 0.001 0.007 Pass Bixafen 0.077 0.002 0.006 Pass Boscalid 0.436 0.029 0.031 Pass Buprofezin 0.044 0.002 0.004 Pass Carbendazim 0.077 0.003 0.006 Pass Cypermethrin 0.110 0.000 0.010 Pass Epoxiconazole 0.190 0.009 0.013 Pass Fenpropidin 0.382 0.003 0.026 Pass Fluopyram 0.262 0.014 0.019 Pass Heptachlor 0.057 0.001 0.002 Pass Isocarbophos 0.046 0.003 0.004 Pass Metrafenone 0.092 0.003 0.007 Pass Pencycuron 0.022 0.001 0.002 Pass Pirimicarb desmethyl 0.049 0.001 0.004 Pass Prothioconazole desthio 0.113 0.004 0.011 Pass Pyraclostrobin 0.101 0.005 0.007 Pass Tebuconazole 0.093 0.001 0.007 Pass Tetramethrin 0.096 0.003 0.000 Pass National Food Institute, Technical University of Denmark Stability test Storage at -18 degrees Storage at room temperature | x1 - yi | ≤ | x1 - yi | ≤ Mean, mg/kg | x1 - yi | 0.3×σ 0.3×σ | x1 - yi | 0.3×σ 0.3×σ Azoxys trobin 0.089 0.001 0.007 Pass 0.001 0.007 Pass Bixafen 0.077 0.002 0.006 Pass 0.001 0.006 Pass Boscalid 0.436 0.029 0.031 Pass 0.001 0.031 Pass Buprofezin 0.044 0.002 0.004 Pass 0.002 0.004 Pass Carbendazim 0.077 0.003 0.006 Pass 0.002 0.006 Pass Cypermethrin 0.110 0.000 0.010 Pass 0.006 0.010 Pass Epoxiconazole 0.190 0.009 0.013 Pass 0.005 0.013 Pass Fenpropidin 0.382 0.003 0.026 Pass 0.020 0.026 Pass Fluopyram 0.262 0.014 0.019 Pass 0.004 0.019 Pass Heptachlor 0.057 0.001 0.002 Pass 0.031 0.002 Fail Isocarbophos 0.046 0.003 0.004 Pass 0.004 0.004 Fail Metrafenone 0.092 0.003 0.007 Pass 0.002 0.007 Pass Pencycuron 0.022 0.001 0.002 Pass 0.017 0.002 Fail Pirimicarb desmethyl 0.049 0.001 0.004 Pass 0.010 0.004 Fail Prothioconazole desthio 0.113 0.004 0.011 Pass 0.003 0.011 Pass Pyraclostrobin 0.101 0.005 0.007 Pass 0.003 0.007 Pass Tebuconazole 0.093 0.001 0.007 Pass 0.006 0.007 Pass Tetramethrin 0.096 0.003 0.000 Pass 0.005 0.000 Pass National Food Institute, Technical University of Denmark National Food Institute, Technical University of Denmark Calculation of assigned values and uncertainty of assigned values • Algoritm A mean of the results from EU laboratories (and EFTA) – Only result from participant that • Reported to add water to the samples before extration or • used mixture of solvent and water or • used ASE • Outliers • Only obvious uncorrect results • Uncertainty • =1.25 *( ) • s* is robust∗ standard deviation (Alg A standard deviation) /√ • n is the number of participants National Food Institute, Technical University of Denmark Assigned values only Assigned values water addition, PESTICIDES mg/kg Azoxystrobin 0.088 Bixafen 0.074 Boscalid 0.414 Buprofezin 0.048 Carbendazim 0.086 Cypermethrin 0.134 Epoxiconazole 0.177 Fenpropidin 0.347 Fluopyram 0.250 Isocarbophos 0.048 Metrafenone 0.088 Pencycuron 0.033 Pirimicarb-desmethyl 0.048 Prothioconazole-desthio 0.149 Pyraclostrobin 0.098 Tebuconazole 0.091 Tetramethrin 0.096 Heptachlor 0.032 National Food Institute, Technical University of Denmark Reported results and false negatives No.