Results of EUPT-CF9 Pesticide residues in maize

Results of EUPT-CF9 Pesticide residues in maize Mette Erecius Poulsen and Susan Strange Herrmann Stuttgart, 1 October 2015

PTs on cereals/feed overview 2007 2008 2009 2010 2011 2012 2013 2014 2015 EUPT-C1 EUPT-C2 EUPT-C3 EUPT-C4 EUPT-C5 EUPT-C6 EUPT-CF7 EUPT-CF8 EUPT-CF9 /SRM2 /SRM4 /SRM6 Test material Wheat flourwheat flour Oat flour Rye flour Rice flour Barley Feed Wheat flour Maize flour no. of participants 64 74 111 118 155 (133) 149 (127) 120 (106) 160 (142) 163 (146) No. of target pesticides 37 55 60 72 104 107 116 116 117 MRM no. of incurred pesticides 3 9 14 13 10 8 19 14 0 no. of spiked pesticides 4 4 3 7 10 4 5 18 SRM no. of incurred pesticides 2 2 2 2 no. of spiked pesticides 1 2 1 7 Total no. of pesticides in test item 10 15 18 19 24 18 23 19 18

3 Organising team at EURL Mette Erecius Poulsen, Senior Chemist Anne Kruse Lykkeberg, Senior Chemist Gitte Andersen, Chemist Susan Strange Herrmann, Chemist Merete B. Ludwigsen, Chemical Technician Lisbet Pilhkjær, Chemical Technician Jens-Ole Frimann, System Developer

Scientific Group Advisory Group Amadeo R. Fernández-Alba André de Kok Antonio Valverde Darinka Štajnbaher Magnus Jezussek Michelangelo Anastassiades Miguel Gamón Ralf Lippold Dr. Sonja Masselter Stewart Reynolds Tuija Pihlström Quality Group Antonio Valverde Stewart Reynolds

Participation Country # labs Country # labs Country # labs Albania 1 France 8 Norway 1 Argentina 1 Germany 23 Poland 15 Australia 1 Greece 3 Portugal 2 Austria 2 Hungary 4 Romania 6 Belgium 3 Iceland 1 Serbia 2 Brazil 2 Indonesia 3 Singapore 1 Bulgaria 3 Ireland 1 Slovakia 2 Croatia 4 Italy 22 Slovenia 3 Cyprus 2 Jamaica 1 Spain 21 Czech Republic 3 Latvia 1 Sweden 2 Denmark 1 Lithuania 1 Switzerland 1 Egypt 1 Luxembourg 1 Tanzania 2 Estonia 1 Netherlands 6 United Kingdom 3 Finland 1 New Zealand 1 Total 163

Participation Country # labs Country # labs Country # labs Albania 1 France 8 Norway 1 Argentina 1 Germany 23 Poland 15 Australia 1 Greece 3 Portugal 2 Austria 2 Hungary 4 Romania 6 Belgium 3 Iceland 1 Serbia 2 Brazil 2 Indonesia 3 Singapore 1 Bulgaria 3 Ireland 1 Slovakia 2 Croatia 4 Italy 22 Slovenia 3 Cyprus 2 Jamaica 1 Spain 21 Czech Republic 3 Latvia 1 Sweden 2 Denmark 1 Lithuania 1 Switzerland 1 Egypt 1 Luxembourg 1 Tanzania 2 Estonia 1 Netherlands 6 United Kingdom 3 Finland 1 New Zealand 1 Total 163

Target Pesticide List 117 pesticides 8 new Diniconazole Ethirimol Fluopyram Isocarbophos Mandipropamid Metolachlor Spiromesifen Terbuthylazine

Acephate Endosulfan-sulfate Isocarbophos Pirimicarb-desmethyl Azinphos-methyl Epoxiconazole Isoprothiolane Pirimiphos-methyl Azoxystrobin Ethion Isoproturon Prochloraz (parent compound only) Bifenthrin Ethirimol Kresoxim-methyl Procymidone Bixafen Fenbuconazole Lambda-cyhalothrin Propiconazole Boscalid Fenhexamid Lindane Prothioconazole-desthio Carbaryl Fenitrothion Linuron Pyraclostrobin Carbendazim Fenpropidin Malaoxon Pyrimethanil Carbofuran Fenpropimorph Malathion Quinoxyfen Carbofuran, 3-hydroxy Fenthion Mandipropamid Spiromesifen Carboxin Fenthion-oxon Metconazole Spiroxamine Chlorfenvinphos Fenthion-oxon-sulfone Methacrifos Tebuconazole Chlorpropham (parent compound only) Fenthion-oxon-sulfoxide Methomyl Tebufenozide Chlorpyrifos Fenthion-sulfone Metolachlor Terbuthylazine Chlorpyrifos-methyl Fenthion-sulfoxide Metrafenone Thiabendazole Clothianidin Fenvalerate and Esfenvalerate Metribuzin Thiacloprid Cyfluthrin (sum of isomers) Fipronil (parent compound only) DDD- p,p' Thiamethoxam Cypermethrin (sum of isomers) Flonicamid DDE- p,p' Thiodicarb Cyproconazole Fludioxonil DDT- o,p' Thiophanate-methyl Cyprodinil Fluopyram DDT- p,p' Triadimefon Deltamethrin-cis Fluquinconazole Omethoate Triadimenol Demeton-S-methylsulfone Flusilazole Oxydemeton-methyl Triazophos Diazinon Flutriafol Paclobutrazol Tricyclazole Dichlorvos Fluxapyroxad Parathion Trifloxystrobin Difenoconazole HCH-alpha Penconazole Trifluralin Diflubenzuron HCH-beta Pendimethalin Triticonazole Dimethoate Hexaconazole Permethrin (sum of isomers) Vinclozolin (parent compound only) Diniconazole Imazalil Phenylphenol-ortho Endosulfan-alpha Imidacloprid Phosphamidon Endosulfan-beta Iprodione Pirimicarb

Maize feed variety Grown in Denmark in 2014 Field treated by Aarhus University, Research Department Flakkebjerg

Pesticides in test material Pesticide Application on cereals in the field Spike in laboratory Formulation or standard Bifenazate x Floramite Cypermethrin x Cyperb Epoxiconazole x Opera Foramsulfuron x MaisTer Iodosulfurum x MaisTer Lambda-cyhalothrin x Karate Pendimethalin x Stomp Propiconazole x Bumper/Tilt Pyraclostrobin x Opera Spirotetramat x Movento Tebuconazole x Folicur Thifensulfuron-methyl x Harmony

Pesticides in test material Pesticide Application on cereals in the field Spike in laboratory Formulation or standard Bifenazate x Floramite Cypermethrin x Cyperb Epoxiconazole x x Opera / Analytical standard Foramsulfuron x MaisTer Iodosulfurum x MaisTer Lambda-cyhalothrin x x Karate Pendimethalin x x Stomp / Analytical standard Propiconazole x x Bumper/Tilt Pyraclostrobin x Opera Spirotetramat x Movento Tebuconazole x Folicur Thifensulfuron-methyl x Harmony

Pesticide Application on cereals in the field Spike in laboratory Formulation or standard Bifenazate Pesticides in test x material Floramite Cypermethrin x Cyperb Epoxiconazole x x Opera / Analytical standard Foramsulfuron x MaisTer Iodosulfurum x MaisTer Lambda-cyhalothrin x x Karate Pendimethalin x x Stomp / Analytical standard Propiconazole x x Bumper/Tilt Pyraclostrobin x Opera Spirotetramat x Movento Tebuconazole x Folicur Thifensulfuron-methyl x Harmony Azoxystrobin x Amistar Carbendazim x Bavistin FL Chlorfenvinphos x Analytical standard Chlorpyrifos-methyl x Reldan Clothianidin x Analytical standard Fluopyram x Analytical standard Isocarbophos x Analytical standard Lindane x Analytical standard Metolachlor x Analytical standard Metribuzin x Analytical standard Spiromesifen x Analytical standard Terbuthylazine x Analytical standard Thiacloprid x Analytical standard Triticonazole x Analytical standard

Spike procedure

Sample shipment Samples were distributed on Monday 20 April 2015 (13 April to Third Countries) Most samples were delivered to EU laboratories on 21 or 22 April 2015

Homogeniety test Mean, mg/kg 2 S s c S 2 s < c Azoxystrobin 0.050 0.00001 0.0000 Pass Carbendazim 0.399 0.00097 0.0018 Pass Chlorfenvinphos 0.041 0.00000 0.0001 Pass Chlorpyrifos-methyl 0.043 0.00000 0.0000 Pass Clothianidin 0.489 0.00116 0.0036 Pass Epoxiconazole 0.050 0.00001 0.0000 Pass Fluopyram 0.089 0.00005 0.0001 Pass Isocarbofos 0.068 0.00001 0.0001 Pass Lambda-cyhalothrin 0.100 0.00001 0.0003 Pass Lindane 0.059 0 0.0002 Pass Metolachlor 0.071 0.00000 0.0002 Pass Test sample no. 0.148 0.00013 0.0003 Pass Pendimethalin 0.043 0.00001 0.0000 Pass Propiconazole 0.148 0.00013 0.0003 Pass Spiromesifen 0.073 0.00000 0.0002 Pass Terbuthylazine 0.079 0.00002 0.0001 Pass Thiacloprid 0.086 0.00003 0.0001 Pass Triticonazole 0.081 0.00003 0.0001 Pass

Stability test Storage at -18 degrees Storage at room temperature Mean, mg/kg x1 - yi 0.3 σ x1 - yi 0.3 σ x1 - yi 0.3 σ x1 - yi 0.3 σ Azoxystrobin 0.049 0.003 0.004 Pass 0.003 0.004 Pass Carbendazime 0.435 0.012 0.034 Pass 0.050 0.034 Fail Chlorfenvinphos 0.050 0.002 0.004 Pass 0.003 0.004 Pass Chlorpyrifos-methyl 0.051 0.002 0.004 Pass 0.003 0.004 Pass Clothianidin 0.534 0.022 0.032 Pass 0.020 0.032 Pass Epoxiconazole 0.054 0.001 0.004 Pass 0.004 0.004 Pass Fluopyram 0.089 0.006 0.007 Pass 0.008 0.007 Fail Isocarbofos 0.079 0.005 0.006 Pass 0.005 0.006 Pass Lambda-cyhalothrin 0.095 0.003 0.007 Pass 0.006 0.007 Pass Lindane 0.074 0.002 0.005 Pass 0.014 0.005 Fail Metolachlor 0.086 0.004 0.006 Pass 0.006 0.006 Pass Metribuzin 0.386 0.001 0.027 Pass 0.075 0.027 Fail Pendimethalin 0.038 0.001 0.003 Pass 0.004 0.003 Fail Propiconazole 0.147 0.003 0.011 Pass 0.002 0.011 Pass Spiromefesin 0.075 0.003 0.005 Pass 0.027 0.005 Fail Terbuthylazine 0.088 0.004 0.006 Pass 0.004 0.006 Pass Thiacloprid 0.094 0.005 0.007 Pass 0.003 0.007 Pass Triticonazole 0.079 0.002 0.006 Pass 0.009 0.006 Fail

Stability test Storage at -18 degrees Storage at room temperature Mean, mg/kg x1 - yi 0.3 σ x1 - yi 0.3 σ x1 - yi 0.3 σ x1 - yi 0.3 σ Azoxystrobin 0.049 0.003 0.004 Pass 0.003 0.004 Pass Carbendazime 0.435 0.012 0.034 Pass 0.050 0.034 Fail Chlorfenvinphos 0.050 0.002 0.004 Pass 0.003 0.004 Pass Chlorpyrifos-methyl 0.051 0.002 0.004 Pass 0.003 0.004 Pass Clothianidin 0.534 0.022 0.032 Pass 0.020 0.032 Pass Epoxiconazole 0.054 0.001 0.004 Pass 0.004 0.004 Pass Fluopyram 0.089 0.006 0.007 Pass 0.008 0.007 Fail Isocarbofos 0.079 0.005 0.006 Pass 0.005 0.006 Pass Lambda-cyhalothrin 0.095 0.003 0.007 Pass 0.006 0.007 Pass Lindane 0.074 0.002 0.005 Pass 0.014 0.005 Fail Metolachlor 0.086 0.004 0.006 Pass 0.006 0.006 Pass Metribuzin 0.386 0.001 0.027 Pass 0.075 0.027 Fail Pendimethalin 0.038 0.001 0.003 Pass 0.004 0.003 Fail Propiconazole 0.147 0.003 0.011 Pass 0.002 0.011 Pass Spiromefesin 0.075 0.003 0.005 Pass 0.027 0.005 Fail Terbuthylazine 0.088 0.004 0.006 Pass 0.004 0.006 Pass Thiacloprid 0.094 0.005 0.007 Pass 0.003 0.007 Pass Triticonazole 0.079 0.002 0.006 Pass 0.009 0.006 Fail

28 days room temperature 14 days room temperature 28 days -18 degrees

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 incorrect results Uncertainty of the assigned values =1.25 *( / ) s* is robust standard deviation (Alg A standard deviation) N is the number of participants

Assigned values only water addition, PESTICIDES mg/kg Azoxystrobin 0.050 Carbendazim 0.452 Chlorfenvinphos 0.048 Chlorpyrifos-methyl 0.054 Clothianidin 0.429 Epoxiconazole 0.050 Fluopyram 0.092 Isocarbophos 0.081 Lambda-cyhalothrin 0.088 Lindane 0.070 Metolachlor 0.085 Metribuzin 0.355 Pendimethalin 0.044 Propiconazole 0.141 Spiromesifen 0.072 Terbuthylazine 0.086 Thiacloprid 0.087 Triticonazole 0.082 Assigned values

Reported results and false negatives No. of reported Pesticide results No. of NA False negatives % results Azoxys trobi n 127 15 4 89 Ca rbenda zi m 108 34 0 76 Chl orfenvi nphos 124 18 2 87 Chl orpyri fos-methyl 130 12 2 92 Clothianidin 102 40 1 72 Epoxi cona zol e 117 25 3 82 Fl uopyra m 87 55 1 61 Is oca rbophos 88 54 7 62 La mbda-cyha l othri n 129 13 5 91 Li nda ne 132 10 3 93 Metol a chl or 96 46 4 68 Metri buzi n 102 40 2 72 Pendi metha l i n 126 16 0 89 Propi cona zol e 126 16 2 89 Spi romes i fen 88 54 3 62 Terbuthyl a zi ne 109 33 0 77 Thiacloprid 107 35 0 75 Tri ticona zol e 107 35 4 75

Reported results and false negatives No. of reported Pesticide results No. of NA False negatives % results Azoxys trobi n 127 15 4 89 Ca rbenda zi m 108 34 0 76 Chl orfenvi nphos 124 18 2 87 Chl orpyri fos-methyl 130 12 2 92 Clothianidin 102 40 1 72 Epoxi cona zol e 117 25 3 82 Fl uopyra m 87 55 1 61 Is oca rbophos 88 54 7 62 La mbda-cyha l othri n 129 13 5 91 Li nda ne 132 10 3 93 Metol a chl or 96 46 4 68 Metri buzi n 102 40 2 72 Pendi metha l i n 126 16 0 89 Propi cona zol e 126 16 2 89 Spi romes i fen 88 54 3 62 Terbuthyl a zi ne 109 33 0 77 Thiacloprid 107 35 0 75 Tri ticona zol e 107 35 4 75

Reported results and false negatives No. of reported Pesticide results No. of NA False negatives % results Azoxys trobi n 127 15 4 89 Ca rbenda zi m 108 34 0 76 Chl orfenvi nphos 124 18 2 87 Chl orpyri fos-methyl 130 12 2 92 Clothianidin 102 40 1 72 Epoxi cona zol e 117 25 3 82 Fl uopyra m 87 55 1 61 Is oca rbophos 88 54 7 62 La mbda-cyha l othri n 129 13 5 91 Li nda ne 132 10 3 93 Metol a chl or 96 46 4 68 Metri buzi n 102 40 2 72 Pendi metha l i n 126 16 0 89 Propi cona zol e 126 16 2 89 Spi romes i fen 88 54 3 62 Terbuthyl a zi ne 109 33 0 77 Thiacloprid 107 35 0 75 Tri ticona zol e 107 35 4 75

Reported results and false negatives No. of reported Pesticide results No. of NA False negatives % results Azoxys trobi n 127 15 4 89 Ca rbenda zi m 108 34 0 76 Chl orfenvi nphos 124 18 2 87 Chl orpyri fos-methyl 130 12 2 92 Clothianidin 102 40 1 72 Epoxi cona zol e 117 25 3 82 Fl uopyra m 87 55 1 61 Is oca rbophos 88 54 7 62 La mbda-cyha l othri n 129 13 5 91 Li nda ne 132 10 3 93 Metol a chl or 96 46 4 68 Metri buzi n 102 40 2 72 Pendi metha l i n 126 16 0 89 Propi cona zol e 126 16 2 89 Spi romes i fen 88 54 3 62 Terbuthyl a zi ne 109 33 0 77 Thiacloprid 107 35 0 75 Tri ticona zol e 107 35 4 75

Reported results and false negatives No. of reported Pesticide results No. of NA False negatives % results Azoxys trobi n 127 15 4 89 Ca rbenda zi m 108 34 0 76 Chl orfenvi nphos 124 18 2 87 Chl orpyri fos-methyl 130 12 2 92 Clothianidin 102 40 1 72 Epoxi cona zol e 117 25 3 82 Fl uopyra m 87 55 1 61 Is oca rbophos 88 54 7 62 La mbda-cyha l othri n 129 13 5 91 Li nda ne 132 10 3 93 Metol a chl or 96 46 4 68 Metri buzi n 102 40 2 72 Pendi metha l i n 126 16 0 89 Propi cona zol e 126 16 2 89 Spi romes i fen 88 54 3 62 Terbuthyl a zi ne 109 33 0 77 Thiacloprid 107 35 0 75 Tri ticona zol e 107 35 4 75

False positive results Lab code Pesticide Concentration mg/kg Determination technique RL, mg/kg 214 Bifenthrin 0.052 GC-MS/MS (QQQ) 226 Thiamethoxam 0.54 LC-MS/MS QQQ 0.02 247 HCH-alpha 0.01 GC-MS/MS (QQQ) 0.01 256 Flonicamid 0.08 LC-MS/MS QQQ 0.01 283 HCH-beta 0.0657 GC-MS/MS (QQQ) 0.01 334 HCH-alpha 0.0457 GC-MSD 0.01 374 HCH-alpha 0.059 GC-MS/MS (QQQ) 0.01 374 HCH-beta 0.081 GC-MS/MS (QQQ) 0.01 406 HCH-beta 0.036 GC-MSD 0.01 < 0.01 mg/kg Lab code Pesticide Concentration mg/kg Determination technique RL, mg/kg 382 Pirimiphos-methyl 0.0046 GC-NPD 0.003

30 Calculations of z-scores For each laboratory/pesticide combination : z = (x-x) / σ x is the result reported by the participant or the specific reporting limit of the lab for those labs not having detected the pesticide present in the test material X is the assigned value, Alg A mean without outliers σ is the target standard deviation obtained by multiplying the median by the FFP RSD of 25% z 2 2 < z < 3 z > 3 Acceptable Questionable Unacceptable

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 119 (94%) 3 (2%) 5 (4%) 127 Azoxystrobin EU and EFTA Laboratories Assigned value: 0.050 Alg A STD: 19% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 4 False Negatives -5,0 269 319 354 372 214 406 373 381 303 332 387 232 365 318 263 273 305 338 350 331 293 212 301 235 257 249 275 215 259 279 320 356 229 282 347 304 225 256 321 352 342 337 312 343 233 217 363 216 386 223 230 299 280 283 385 258 324 213 300 221 346 222 246 341 236 274 330 336 298 351 378 285 297 326 252 254 284 260 287 268 314 281 310 376 334 362 290 325 327 329 262 239 379 340 294 253 231 276 245 247 288 361 237 265 234 307 228 240 339 344 250 355 241 242 272 278 368 291 271 277 306 335 309 302 226 408 374

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 98 (91%) 5 (5%) 5 (5%) 108 Carbendazim EU and EFTA Laboratories Assigned value: 0.452 Alg A STD: 28% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 0 False Negatives -5,0 329 361 373 288 247 387 214 212 278 273 293 232 276 217 331 300 347 356 306 350 320 365 259 225 381 216 280 226 279 223 235 304 318 245 275 246 249 229 406 240 260 252 272 332 343 284 355 346 362 231 213 233 351 277 253 310 298 340 330 234 256 282 269 363 228 321 290 344 222 309 377 281 265 254 327 294 339 378 352 271 262 341 242 215 258 338 305 334 237 312 285 379 268 283 323 385 274 302 386 250 241 314 263 236 301 303 291 307

5,0 Water added No water added Not specified ASE Carbendazim EUPT-CF8 Acceptable Questionable Unacceptable Number of labs 81 (84%) 5 (4%) 11 (12%) 97 4,0 Assigned value: 0.073 mg/kg 3,0 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 * False negatives -5,0 56 55 140 99 95 97 33 81 104 136 38 74 40 35 110 145 123 28 837 44 17 105 143 107 30 324 141 87 161 53 29 147 26 156 91 122 19 160 13 11 82 16 126 3 43 109 157 59 65 845 42 49 111 70 14 47 88 121 80 27 64 120 124 18 482 67 76 45 92 98 21 63 20 61 112 89 159 34 31 66 150 134 142 8 78 22 106 36 39 73 46 96 71

5,0 Water added No water added Not specified ASE Carbendazim EUPT-CF7 Acceptable Questionable Unacceptable Number of labs 59 4 6 69 4,0 Assigned value: 0.252 mg/kg 3,0 2,0 1,0 Low solubility, In ethyl acetate 0.135 mg/ml check if standard is dissolved z-scores 0,0-1,0-2,0-3,0-4,0-5,0 054 002 120 056 032 126 128 068 037 107 014 034 036 060 074 020 028 007 105 009 087 063 050 125 071 127 101 064 092 043 121 059 061 094 132 029 076 051 016 086 025 075 093 083 065 017 005 096 039 023 067 027 033 124 069 123 030 035 070 021 113 026 015 073 019 085 006 122 055

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 98 (91%) 5 (5%) 5 (5%) 108 Carbendazim EU and EFTA Laboratories Assigned value: 0.452 Alg A STD: 28% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 0 False Negatives -5,0 329 361 373 288 247 387 214 212 278 273 293 232 276 217 331 300 347 356 306 350 320 365 259 225 381 216 280 226 279 223 235 304 318 245 275 246 249 229 406 240 260 252 272 332 343 284 355 346 362 231 213 233 351 277 253 310 298 340 330 234 256 282 269 363 228 321 290 344 222 309 377 281 265 254 327 294 339 378 352 271 262 341 242 215 258 338 305 334 237 312 285 379 268 283 323 385 274 302 386 250 241 314 263 236 301 303 291 307

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 119 (96%) 2 (2%) 3 (2%) 124 Chlorfenvinphos EU and EFTA Laboratories Assigned value: 0.048 Alg A STD: 18% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 2 False Negatives -5,0 280 406 214 303 331 332 329 235 350 387 301 356 305 245 232 254 365 226 249 276 318 229 293 310 246 320 335 300 213 362 212 257 278 263 279 285 217 259 379 321 326 277 363 344 378 281 231 282 347 275 343 225 265 304 338 346 361 354 319 250 252 260 368 253 290 274 345 324 223 237 256 288 283 216 258 373 314 284 330 352 348 312 327 247 342 385 386 372 295 294 228 233 291 215 222 273 298 240 336 268 307 381 230 234 351 297 309 355 236 241 272 306 262 325 239 221 242 337 271 339 302 269 376 340

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 119 (92%) 8 (6%) 3 (2%) 130 Chlorpyrifos-methyl EU and EFTA Laboratories Assigned value: 0.054 Alg A STD: 18% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 2 False Negatives -5,0 278 279 333 303 232 324 223 378 280 246 293 212 249 263 276 321 365 229 331 226 257 273 320 387 214 235 347 300 213 356 237 318 350 250 254 282 301 275 342 352 372 362 305 259 225 231 337 295 334 256 304 338 215 252 277 351 216 258 345 281 284 283 319 222 242 247 330 346 386 315 312 373 274 368 253 217 299 363 379 310 233 234 298 382 272 285 344 343 326 327 361 239 290 297 348 288 306 381 241 287 294 309 325 260 355 335 268 271 262 221 291 307 230 376 336 339 265 385 245 228 240 236 340 302 408 314 341 329 354 269

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 97 (95%) 3 (3%) 2 (2%) 102 Clothianidin EU and EFTA Laboratories Assigned value: 0.429 Alg A STD: 21% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 1 False Negatives -5,0 226 406 280 276 377 235 214 373 332 318 350 293 249 217 256 341 331 212 320 340 356 247 231 216 269 279 343 362 263 408 275 387 288 301 339 361 225 259 314 284 365 233 291 223 215 232 283 368 252 321 282 300 260 312 258 253 306 241 262 245 310 285 305 351 352 281 327 265 355 234 379 334 363 213 294 386 254 272 344 304 303 242 240 338 329 229 309 268 277 222 250 237 378 273 290 302 298 307 274 271 236 228

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 113 (97%) 1 (1%) 3 (3%) 117 Epoxiconazole EU and EFTA Laboratories Assigned value: 0.050 Alg A STD: 18% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 3 False Negatives -5,0 249 329 372 381 214 387 406 332 303 331 276 305 318 293 217 263 377 233 212 314 279 356 226 232 254 361 386 235 257 269 304 342 216 341 275 298 301 225 300 350 231 287 258 252 283 284 282 330 337 376 229 365 343 256 265 338 324 230 274 246 260 259 385 213 273 351 285 223 280 346 239 297 378 312 325 373 215 291 362 281 221 321 334 268 250 306 253 310 234 237 307 363 379 290 327 320 245 240 262 272 294 277 355 344 247 271 309 336 340 241 302 339 368 335 228 242 236

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 86 (99%) 0 (0%) 1 (1%) 87 Fluopyram EU and EFTA Laboratories Assigned value: 0.092 Alg A STD: 17% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 1 False Negatives -5,0 338 406 332 318 331 386 235 279 343 263 372 350 252 275 216 217 233 259 212 361 237 282 304 352 231 284 225 226 254 301 273 288 321 258 260 256 320 249 298 300 213 346 283 281 215 265 291 241 340 222 330 362 310 327 314 253 363 324 268 378 228 234 355 285 305 339 247 262 379 294 245 344 271 309 242 307 240 306 229 272 329 236 250 368 274 290 365

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 79 (90%) 2 (2%) 7 (8%) 88 Isocarbophos EU and EFTA Laboratories Assigned value: 0.081 Alg A STD: 16% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 7 False Negatives -5,0 214 256 314 329 338 386 406 331 365 305 350 263 235 250 225 265 279 387 275 259 318 368 233 351 378 226 246 281 298 215 249 252 330 284 282 320 216 242 213 300 363 324 229 237 355 362 260 304 339 346 301 283 327 332 344 285 253 372 379 352 385 294 222 280 274 217 231 234 291 340 228 343 262 254 258 240 271 307 361 310 241 245 290 309 273 268 306 236

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 121 (94%) 2 (2%) 6 (5%) 129 Lambda-cyhalothrin EU and EFTA Laboratories Assigned value: 0.088 Alg A STD: 20% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 5 False Negatives -5,0 269 280 329 336 372 354 406 331 228 258 332 365 318 303 338 374 242 249 276 299 273 263 279 324 281 305 293 233 277 373 250 247 387 262 212 386 252 235 408 232 284 231 246 254 361 309 351 343 271 306 352 213 259 350 348 274 275 304 346 319 223 381 345 215 217 256 283 379 216 290 315 222 225 261 245 272 237 285 253 260 239 362 229 376 288 291 347 240 320 335 307 313 301 342 297 339 236 363 294 310 378 234 295 326 355 321 327 287 368 325 385 230 340 268 221 265 344 298 337 356 257 282 341 314 241 300 302 330 226

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 120 (91%) 9 (7%) 3 (2%) 132 Lindane EU and EFTA Laboratories Assigned value: 0.070 Alg A STD: 19% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 3 False Negatives -5,0 278 283 334 333 406 331 303 232 342 248 343 252 309 297 325 332 284 299 313 239 346 221 222 271 382 350 352 250 376 347 253 249 320 318 227 276 337 387 257 251 315 345 338 361 381 293 230 235 212 215 231 263 223 368 254 279 386 365 305 319 274 268 256 275 277 341 324 225 237 273 356 295 226 259 213 246 282 304 258 330 300 217 281 363 372 290 288 362 285 312 348 234 247 302 294 327 287 301 379 260 321 245 353 385 241 310 344 261 272 314 265 228 307 262 326 354 355 329 242 351 306 339 233 291 374 240 336 340 236 378 229 298

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 89 (93%) 1 (1%) 6 (6%) 96 Metolachlor EU and EFTA Laboratories Assigned value: 0.085 Alg A STD: 18% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 4 False Negatives -5,0 235 250 319 373 214 338 263 354 378 379 332 318 351 212 226 343 252 293 257 265 350 229 284 279 281 246 301 249 232 273 276 331 233 275 320 258 259 274 256 282 387 330 362 304 363 231 287 223 213 300 352 361 290 217 254 321 216 368 386 324 285 372 241 283 327 222 247 225 253 355 305 271 245 228 234 291 278 310 344 340 262 268 237 309 215 365 408 294 240 242 306 272 307 329 236 374

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 98 (96%) 0 (0%) 4 (4%) 102 Metribuzin EU and EFTA Laboratories Assigned value: 0.355 Alg A STD: 17% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 2 False Negatives -5,0 306 314 215 246 232 372 347 235 247 354 332 331 381 257 318 265 216 222 249 259 361 303 387 365 351 293 263 283 258 352 250 324 256 300 229 279 226 233 305 363 321 212 225 330 213 275 217 281 350 274 260 282 304 319 285 254 278 284 310 237 231 277 276 335 288 291 252 299 379 362 368 253 223 240 262 271 320 338 234 245 339 294 273 343 378 290 327 386 241 309 355 344 268 329 340 326 236 301 228 307 242 385

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 119 (94%) 6 (5%) 1 (1%) 126 Pendimethalin EU and EFTA Laboratories Assigned value: 0.044 Alg A STD: 19% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 0 False Negatives -5,0 406 303 338 330 381 214 263 293 232 247 318 356 229 301 212 276 332 321 341 299 305 320 235 295 300 324 249 254 331 348 257 273 213 373 246 361 253 259 284 252 215 256 277 280 346 362 343 225 231 275 342 352 368 372 250 386 226 237 298 347 351 294 285 314 350 288 334 377 274 281 379 221 304 279 345 282 387 327 283 335 216 365 378 233 241 271 239 262 355 245 230 325 265 337 339 278 363 234 291 306 217 222 228 297 310 326 344 309 260 272 336 287 258 240 374 268 290 242 269 408 340 385 236 307 329 354

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 121 (96%) 1 (1%) 4 (3%) 126 Propiconazole EU and EFTA Laboratories Assigned value: 0.141 Alg A STD: 19% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 2 False Negatives -5,0 269 354 406 306 372 214 303 226 276 331 332 387 235 293 350 342 376 254 305 356 212 343 257 229 246 249 318 381 252 263 282 338 232 250 225 279 351 274 326 283 231 284 341 275 386 215 298 300 256 347 230 329 324 365 379 221 314 258 259 301 330 346 236 361 273 287 281 337 352 233 217 297 216 247 260 334 239 385 325 377 265 245 290 268 280 355 362 304 378 321 312 320 253 213 344 363 291 327 222 237 271 272 373 234 340 223 262 285 310 309 294 242 288 307 408 336 241 339 319 277 368 228 335 240 278 299

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 83 (93%) 1 (1%) 4 (6%) 88 Spiromesifen EU and EFTA Laboratories Assigned value: 0.072 Alg A STD: 22% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 3 False Negatives -5,0 214 242 298 232 249 331 263 332 406 338 343 225 334 235 254 260 212 304 216 284 329 324 252 280 318 320 226 301 281 259 213 306 233 234 247 258 279 314 362 290 275 350 246 273 305 215 379 346 363 274 327 300 217 237 222 231 291 282 223 285 340 387 250 352 245 355 241 253 385 283 294 344 268 378 265 386 229 272 271 361 240 310 309 228 262 365 236 307

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 106 (97%) 1 (1%) 2 (2%) 109 Terbuthylazine EU and EFTA Laboratories Assigned value: 0.086 Alg A STD: 17% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 0 False Negatives -5,0 261 406 214 343 252 276 354 213 332 293 280 212 233 335 331 318 226 351 249 378 377 320 365 300 284 232 387 279 363 321 259 231 273 319 372 373 298 216 225 283 246 282 330 350 352 362 260 271 256 338 346 285 215 301 281 235 287 254 291 304 361 274 234 258 229 263 217 290 237 247 253 222 262 327 268 385 242 336 344 265 275 307 355 408 250 379 294 241 305 386 245 309 310 278 277 228 339 326 240 257 272 368 314 288 306 340 329 236 223

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 103 (96%) 1 (1%) 3 (3%) 107 Thiacloprid EU and EFTA Laboratories Assigned value: 0.087 Alg A STD: 20% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 0 False Negatives -5,0 214 406 387 373 293 332 386 245 247 318 341 356 301 222 276 212 249 263 330 321 232 343 252 269 351 331 283 352 235 338 279 350 217 258 284 368 275 365 225 288 223 300 347 273 282 256 280 320 231 340 259 285 385 233 303 215 291 361 226 362 305 254 339 260 348 234 237 229 265 281 312 250 378 253 327 298 304 314 334 268 242 213 216 228 309 379 294 310 408 278 344 363 241 306 236 272 271 240 336 290 355 277 329 274 307 262 377

5,0 4,0 3,0 Acceptable Questionable Unacceptable Number of labs Water added No water added Not specified ASE 98 (92%) 4 (4%) 5 (5%) 107 Triticonazole EU and EFTA Laboratories Assigned value: 0.082 Alg A STD: 18% mg/kg 2,0 1,0 z-scores 0,0-1,0-2,0-3,0-4,0 4 False Negatives -5,0 254 269 372 377 332 361 214 325 239 221 373 230 297 276 293 263 337 318 343 235 279 232 356 331 212 275 284 283 222 330 252 350 249 231 301 225 320 216 226 362 265 282 247 233 304 352 312 258 378 300 246 338 387 281 215 223 298 305 334 257 217 228 280 229 256 291 314 385 310 365 253 285 274 237 245 327 321 290 234 259 260 355 262 339 368 250 268 344 386 294 379 336 271 307 363 240 242 213 273 272 340 241 309 236 329 406 374

Alg. A RSD 0,25 0 Azoxystrobin Carbendazim Chlorfenvinphos Chlorpyrifos-methyl Clothianidin Epoxiconazole Fluopyram Isocarbophos Lambda-cyhalothrin Lindane Metolachlor Metribuzin Pendimethalin Propiconazole Spiromesifen Terbuthylazine Thiacloprid Triticonazole

Acceptable, questionable and unacceptable results No. of reported results Assigned values mg/kg Acceptable % Questionable % Unacceptable % False negatives % Azoxys trobi n 127 0.050 94 2 4 3 Ca rbenda zi m 108 0.452 91 5 5 0 Chl orfenvi nphos 124 0.048 96 2 2 2 Chl orpyri fos-methyl 130 0.054 92 6 2 2 Clothianidin 102 0.429 95 3 2 1 Epoxi cona zol e 117 0.050 97 1 3 3 Fl uopyra m 87 0.092 99 0 1 1 Is oca rbophos 88 0.081 90 2 8 8 La mbda-cyha l othri n 129 0.088 94 2 5 4 Li nda ne 132 0.070 91 7 2 2 Metol a chl or 96 0.085 93 1 6 4 Metri buzi n 102 0.355 96 0 4 2 Pendi metha l i n 126 0.044 94 5 1 0 Propi cona zol e 126 0.141 96 1 3 2 Spi romes i fen 88 0.072 94 1 5 3 Terbuthyl a zi ne 109 0.086 97 1 2 0 Thi a cl opri d 107 0.087 96 1 3 0 Tri ticona zol e 107 0.082 92 4 5 4

Acceptable, questionable and unacceptable results

Catagory A laboratories and combined z-scores To be classified as Category A laboratory the labs had to report at least 90% of the pesticide present in the test material ( 17 pesticide residues) and report no false positive. Evaluation of the overall performance, the Average of the Squared z-score (AZ2) are calculated: AZ 2 n i 1 n Z 2 i z 2 Good 2 < z < 3 Satisfactory z > 3 Unsatisfactory

5,0 OFL NRL Catagory A: 80 labs (56%) 4,0 Good: 96% Satisfactory: 3 % Unsatisfactory: 3% 3,0 2,0 1,0 0,0 362 281 253 231 304 285 260 327 352 363 259 282 284 234 275 216 225 213 237 321 222 254 217 233 258 320 215 379 252 294 310 300 245 355 279 265 344 305 330 343 290 273 268 350 386 274 368 339 250 212 378 229 272 249 271 365 235 298 309 338 314 318 387 241 240 340 361 306 301 228 263 232 291 332 262 331 242 329 236 307

EUPT-CF10 EUPT Tentative date Matrix FV-18 February 2016 Spinach CF-10 March 2016 Rye SRM-11 April 2016 Spinach AO-11 April-May 2016 Pork fat

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