BENZOVINDIFLUPYR (261)

Transcription

1 145 BENZOVINDIFLUPYR (261) First draft prepared by Mr Canping Pan, Department of Applied Chemistry, China Agricultural University, Beijing , P R China EXPLANATION Benzovindiflupyr was scheduled for residue evaluation for new uses and other evaluations by the 2016 JMPR at the 47 th and 48 th sessions of the CCPR (2015, 2016). Benzovindiflupyr is a broadspectrum fungicide first evaluated by JMPR in 2013 (Toxicology) and 2014 (Residues). The toxicological review established an ADI of mg/ bw/day and an ARfD of 0.1 mg/ bw. A residue definition of benzovindiflupyr was recommended for plant and animal commodities, for both compliance with MRLs and estimation of dietary intake. The residue is fat soluble. In 2014, the JMPR evaluated soya bean and livestock feeding studies. An MRL of 0.05 mg/ for soya bean (dry) was proposed based on supervised field trials in Brazil, supporting the cgap of Paraguay. MRLs for animal origins were recommended for edible offal (mammalian), eggs, mammalian fats, meat (from mammals other than marine mammals), milks, and poultry products. The current Meeting received new information on use patterns for benzovindiflupyr in multiple crops (including wheat, barley, grapes, apple, pear, pulses (beans, peas), soya beans (dry), tomato, peppers, cucumber, summer squash, cantaloupe, maize(corn), cotton, peanuts, potatoes, sugarcane, rapeseed, and coffee) supported by additional analytical methods, storage stability data and supervised field trials. Soya bean data from US trials were also received, which contain higher residues than in Brazil trials evaluated by 2014 JMPR. RESIDUE ANALYSIS Analytical methods Analytical methods for benzovindiflupyr in food and feedstuffs of plant origin were evaluated by the 2014 JMPR. Other than sugar cane and peanuts, the residues trials were analysed using methods GRM042.03A (JMPR 2014 evaluation report, page 89-91) and GRM042.04A (JMPR 2014 evaluation report, page 91-95). The sugarcane analyses along with its processed products, cereal grains, were conducted with method POPIT MET.125. Peanuts and some other matrices were conducted with method POPIT MET.133. The two methods were shown to be suitable for determination of benzovindiflupyr, with its procedure improved upon method GRM042.03A. Method POPIT MET.125 Finely-ground samples by homogenisation are extracted with acetonitrile: water (8:2, v:v) and then centrifuged. For the determination of benzovindiflupyr in sugarcane molasses, bagasse and sugar, an aliquot of the extract is diluted in water and purified by soil-phase extraction (Oasis HLB), eluting in acetonitrile. For the determination of benzovindiflupyr in sugarcane stalks and juice, an aliquot is removed from the extract and evaporated to remove acetonitrile. Further, hydrochloric acid (1M) is added and the aliquot partitioned against cyclohexane. The collected organic phases, either from partition or column elution are evaporated, re-dissolved in acetonitrile: water (1:1, v:v) and centrifuged or filtered (0.22 µm) for LC-MS/MS determination of benzovindiflupyr. Residues are quantified using HPLC separation and triple-quadrupole mass spectrometry (LC-MS/MS) detection. LOQs in various matrices were 0.01mg/.

2 Benzovindiflupyr 146 Table 1 Method validation data for method POPIT MET.125 measuring benzovindiflupyr in sugar cane, its processed fractions and cereal grain matrices Matrix Fortification Level (mg/) n Recovery range (%) Recovery, mean (%) RSD (%) Sugar cane Cane juice Cane molasses Cane bagasse Sugar Wheat Oat Barely Green corn Dried corn Corn plant Method POPIT MET.133 Benzovindiflupyr residues are extracted from finely-ground samples by homogenisation with acetonitrile: water (8:2, v:v) and then centrifuged. An aliquot is removed from the extract and evaporated to remove acetonitrile. Hydrochloric acid (1M) is then added and the aliquot partitioned against hexane, collecting both the organic and aqueous phases. The combined organic phases are evaporated, re-dissolved in acetonitrile: water (1:1, v:v) and centrifuged for LC-MS/MS determination of benzovindiflupyr. Residues are quantified using HPLC separation and triple-quadrupole mass spectrometry (LC-MS/MS) detection. LOQs in various matrices were 0.01 mg/. Table 2 Method validation data for measuring benzovindiflupyr in peanut and other matrices Matrix Fortification Level (mg/) n Recovery range (%) Recovery, mean (%) RSD (%) Peanut Bean Sunflower Cotton Coffee beans Roasted coffee Coffee ground Coffee extract

3 147 Benzovindiflupyr Matrix Fortification Level (mg/) n Recovery range (%) Recovery, mean (%) RSD (%) Concentrated coffee Instant coffee Stability of pesticides in stored analytical samples The storage stability of benzovindiflupyr in raw and processed plant commodities, and in animal commodities was evaluated by the 2014 JMPR. No additional storage stability data were submitted to the Meeting. Storage stability studies showed that benzovindiflupyr were stable for at least 24 months at - 18ºC in crop commodities representative of the high water, high acid, high starch, high protein and high oil commodity groups as well as in wheat straw. Benzovindiflupyr residues were stable for at least 24 months at -10 ºC in various processed commodities: flour (maize, soya), meal (maize), oil (maize, soya), soymilk, dried fruits (grape, apple) and fruit juice (apple). USE PATTERN Benzovindiflupyr, belonging to the pyrazole carboxamide class, is a broad-spectrum fungicide and is used especially for its effect against rust. Benzovindiflupyr acts as an inhibitor of the fungal complex II respiratory chain, where it inhibits the succinate dehydrogenase enzyme by blocking the ubiquinone-binding sites in the mitochondrial complex. Benzovindiflupyr is a registered fungicide in several countries including Brazil, Canada, and the. The registered labels were submitted in the original language as well as their English translations. The information available to the Meeting on registered uses of benzovindiflupyr is summarized in Table 3. Table 3 List of country label uses of benzovindiflupyr Crop (group/commodity) Country/ Region Formulation type (benzovindiflupyr guarantee) Application Method Max. no. Min. interval between applications (days) Max. rate (g ) Pome fruits Canada 78g/L EC Foliar % EC Foliar a PHI (days) Grape and small Canada 100g/L EC Foliar fruit vine climbing 78 g/l EC % EC Foliar Cucurbits Canada 78g/L EC Foliar % EC Foliar Fruiting vegetables Canada 78g/L EC Foliar % EC Foliar Sweet corn Canada 100g/L EC Foliar % EC Foliar Pulses (except soya Canada 100g/L EC Foliar bean) 10.27% EC Foliar Soya bean (dry) Canada 100g/L EC Foliar ; 1d for forage and hay 150g/ WG Foliar Potato Canada 100g/L EC Foliar % EC In- 1 NA 100 NA

4 Benzovindiflupyr 148 Crop (group/commodity) Country/ Region Formulation type (benzovindiflupyr guarantee) Application Method Max. no. Min. interval between applications (days) Max. rate (g ) PHI (days) Cereals (including wheat, barley, oat, rye and triticale) furrow Canada 100g/L EC Foliar Feekes for forage and hay 10.27% EC Foliar Feekes 10.5 Maize Canada 100g/L EC Foliar % EC Foliar Sugar cane Brazil 150g/ WG Foliar Cotton 10.27% EC Foliar Peanut Brazil 150g/ WG Foliar % EC Foliar % EC Foliar Rape seed Canada 100g/L EC Foliar 1 NA % EC Foliar 1 NA Coffee Brazil 50g/ EC Foliar a A fourth application is allowed where 12 or more fungicide applications are made. RESIDUES RESULTING FROM SUPERVISED TRIALS ON CROPS Residue levels were reported as measured. Application rates were always reported as benzovindiflupyr equivalents. When residues were not detected they are shown as below the LOQ, e.g., mg/. Application rates, spray concentrations and mean residue results have generally been rounded to two significant figures. HR and STMR values from the trials conducted according to maximum GAP have been used for the estimation of maximum residue levels. These results are underlined. Laboratory reports included method validation including batch recoveries with spiking at residue levels similar to those occurring in samples from the supervised trials. Dates of analyses or duration of residue sample storage were also provided. Field reports provided data on the sprayers used and their calibration, plot size, residue sample size and sampling date. Although trials included control plots, no control data are recorded in the tables except where residues in control samples exceeded the LOQ. Residue data are recorded unadjusted for % recovery. Commodity Indoor/Outdoor Treatment Countries Table Apple Outdoor Foliar Canada, 4 Pear Outdoor Foliar Canada, 5 Grapes Outdoor Foliar 6 Cucumber Outdoor Foliar 7 Summer squash Outdoor Foliar 8 Cantaloupe Outdoor Foliar 9

5 149 Benzovindiflupyr Commodity Indoor/Outdoor Treatment Countries Table Peppers Outdoor Foliar 10 Tomato Outdoor Foliar 11 Sweet corn Outdoor Foliar 12, 26, 27 Pulses (except soya bean) Outdoor Foliar Canada, 13, 28, 29 Soya bean (dry) Outdoor Foliar 14, 30, 31 Potato Outdoor Foliar, Soil, infurrow 15 Barley Outdoor Foliar Canada 16, 17,32-35 Maize Outdoor Foliar 18, 36, 37 Wheat Outdoor Foliar Canada 19, 20, Sugar cane Outdoor Foliar Brazil 21 Cotton seed Outdoor Foliar 22, 44 Peanut Outdoor Foliar, Soil Brazil, 23, 45 Rape seed Outdoor Foliar Canada 24 Coffee Outdoor Foliar Brazil 25 Table 4 Residues of benzovindiflupyr in apple from field trials in Canada and Location, Application Residues, mg/ Report; (remarks) Year (variety) Form. no cgap: , PHI: 30d North Rose, NY (Cortland) North Rose, NY (Ida Red) Hereford, PA (Starkrimson) BBCH [last application date] 81 [07/29/10] 85 [08/26/10] Sample DALA Benzovindiflupyr Apple Apple Apple , () 0.011, (0.01), (0.039) 0.028, (0.021) 0.062, (0.074) 0.057, (0.057) TK E TK E TK E

6 Benzovindiflupyr 150 Location, Application Residues, mg/ Report; (remarks) Year (variety) Form. no cgap: , PHI: 30d Alto, GA (Arkansas, Black) Conklin, MI (Red Delicious) Conklin, MI (Golden Delicious) Madera, CA (Fuji) Los Molinos, CA (Summer field) Ephrata, WA (Red Delicious) Ephrata, WA (Breabum) Hood River, OR (Jonagold) Hood River, OR (Honey Crisp) BBCH [last application date] Sample DALA Benzovindiflupyr 78 Apple Apple Apple [08/20/10] 85 Apple [08/20/10] Apple Apple [09/08/10] 87 Apple [09/14/10] 77 Apple [08/26/10] 77 Apple [08/16/10] , , , (0.067) 0.080, (0.067) 0.018, (0.019), 0.01 (0.01) 0.087, (0.069) 0.034, () 0.17, 0.15 (0.16) 0.033, () 0.034, (0.034) 0.012, (0.016) 0.074, () 0.053, (0.057) 0.12, 0.069, ( 0.074) 0.086, , (0.096) , (0.061) 0.019, TK E TK C TK C TK E TK W TK W TK W TK W TK W

7 151 Benzovindiflupyr Location, Application Residues, mg/ Report; (remarks) Year (variety) Form. no cgap: , PHI: 30d Madera. CA (Fuji) Canada, Berwick, NS (McIntosh) Canada, St. George, ON (Empire) Canada, Branchton, ON (McIntosh) Canada, Branchton, ON (Imperial Gala) Canada, Okanagan Falls, BC (McIntosh) EC b 4 EC b 4 EC b 4 EC b 4 EC b BBCH [last application date] Sample DALA Benzovindiflupyr 85 Apple Apple Apple [25 Aug 11] [25 Aug 11] 61 Apple Apple Apple 30 a EC 150g/L; b EC 100g/L DALA: days after last treatment Analytical method: GRM042.03A, Benzovindiflupyr. Mean = 98%, RSD = ± 9.8%, (n = 18 in 0.01 mg/ range) , () 0.013, (0.012),0.057 (0.048) 0.029, (0.022) 0.036, () 0.028,0.025 (), () 0.025, (0.023) 0.033, (0.042) 0.026, (0.031) 0.036, (0.031) 0.013, () TK TK CER05906/11 T CER05906/11 T CER05906/11 T CER05906/11 T CER05906/11 T Table 5 Residues of benzovindiflupyr in pear from field trials in Canada and Location, Application Residues, mg/ Report; (remarks) Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr cgap: , PHI: 30d Orefield, PA (Bartlett) Pear , (0.021), (0.01) TK E Lindsay, Pear , (0.062) TK W

8 Benzovindiflupyr 152 Location, Application Residues, mg/ Report; (remarks) Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr cgap: , PHI: 30d CA (Olympic) Madera. CA (Asian Pear, Hosui)) Ephrata, WA (Concorde) Ephrata, WA (Bartlett) Hood River, OR (Red d Anjou) Ephrata, WA (Concorde) Canada, Beamsville, ON (Bosc) Canada, Simcoe, ON (Bartlett) Canada, Beamsville, ON (D Anjou Canada, St. Catharines, ON (Bartlett) Canada, Okanagan Falls, BC (Bartlett) EC b 4 EC b 4 EC b 4 EC b 4 EC b Pear [08/20/10] 80 [08/06/10] , (0.035) 60 Pear Pear Pear [08/29/11] [17 Aug 11] 60 Pear Pear Pear [17 Aug 11] 60 Pear Pear Pear 31 59, (0.067) 0.011, (0.014) 0.11, () 0.025, (0.028) 0.082, 0 (0.091), () 0.084, (0.087) 0.026, (0.023) 0.019, (0.026) 0.017, (0.016) 0.042, () 0.022, (0.019) 0.064, (0.057), (0.025), (0.036) 0.014, (0.013) 0.062, (0.059) 0.011, (0.011) 0.036, (0.044) 0.019, (0.023) 1.9 TK E TK W TK W TK W TK TK CER05907/11 T CER05907/11 T CER05907/11 T CER05907/11 T CER05907/11 T a EC 150g/L b EC 100g/L DALA: days after last treatment Analytical method: GRM042.03A, Benzovindiflupyr. Mean = 98%, RSD = ± 9.8, (n = 18 in 0.01 mg/ range)

9 153 Benzovindiflupyr Table 6 Residues of benzovindiflupyr in grapes from field trials in Location, Application Residues, mg/ Report; (remarks) Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr cgap: Canada, 3, PHI: 21d Dundee, NY (Concord, ) Dundee, NY (Vidal,) Artios, CA (Rubi Red) Kerman, CA (Thompson Seedless) Hickman, CA (Chardonnay) [08/31/2010] 85 [09/24/2010] Grapes Grapes Grapes Grapes Grapes , 0.27 (0.23) 0.15, 0.17 (0.16) 0.23, 0.48 (0.35) 0.36, 0.26 (0.31) 0.59, 0.73 (0.66) 0.81, 0.72 (0.77) 0.11, 0.11 (0.11) 0.25, 0.21 (0.23) , , 0.34 TK E TK E TK W TK W TK W Delano, CA (Thompson Seedless) Madera, CA (Thompson Seedless) Lindsay, CA (Crimson) Fresno, CA (Thompson Seedless) Madera, CA (Thompson Seedless) Ephrata, WA (White Riesling) Grapes [08/09/2010] 45 Grapes Grapes [08/13/2010] 85 [08/13/2010] 85 [09/16/2010] 45 Grapes Grapes Grapes , 0.11 () 0.061, (0.052) 0.14, 0.14 (0.14) 0.12, (0.11) 0.43, 0.38 (0.41) 0.39, 0.30 (0.35) , (0.089) , (0.084), 0.23 (0.17) 0.12, 0.14 (0.13) 0.55, 0.55 (0.55) 0.40, 0.39 (0.40) TK W TK W TK W TK E TK E TK W

10 Benzovindiflupyr 154 Location, Application Residues, mg/ Report; (remarks) Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr cgap: Canada, 3, PHI: 21d Ephrata, WA (Chardonnay) Fresno, CA (Ruby Red) Fresno, CA (Thompson Seedless) Dundee, NY (Concord) Madera, CA (Thompson Seedless) Templeton, CA (Marsanne) WG b 4 WG b 4 EC a 4 WG b [09/02/2010] 83 [08/25/ [08/25/2011] 83 [08/31/2011] 81 [08/01/2011] a EC 150g/L; b WG 45g/L DALA: days after last treatment Analytical method: GRM042.03A, Benzovindiflupyr. Mean = 103%, RSD = ±12% (n = 16 in 0.01 mg/) Grapes Grapes Grapes , 0.35 (0.42) 0.27, 0.25 (0.26), (0.039) 0.043, () 0.15, 0.16 (0.16), (0.093) Grapes , 0.44, 0.31 (0.39) , 0.38, 0.34 (0.37) Grapes , 0.17, 0.11 (0.15) , 0.14, 0.15 (0.14) 81 Grapes , 0.087, (0.079) ,, (0.11) TK W TK TK TK TK TK TK TK TK TK TK

11 155 Benzovindiflupyr Table 7 Residues of benzovindiflupyr in cucumber from field trials in Location, Application Residues, mg/ Report; (remarks) Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr cgap: 4, PHI: 0d Chula, GA (Thunder) Cucumber , 0, 0 (0.013) TK TK WG b , 0.012, (0.013) Suffolk, NC (Marketer) Cucumber 0 0, (0.010) TK TK Hobe Sound, FL (Impact) Cucumber , 0.047, (0.052) TK TK WG b , 0.039, (0.049) Northwood, ND (Marketmore 76) WG b Cucumber 0 0, 0, 0 (0) 0 0, 0, 0 (0) TK TK Campbell, MN (Speedway) Cucumber , (0.018) TK TK Hinton, OK (Calypso) Cucumber 0, (0.033) TK TK a EC 100g/L; b WG 45g/L DALA: days after last treatment Analytical method: GRM042.03A, Benzovindiflupyr. Mean = 103%, RSD = ±12% (n = 16 in 0.01 mg/)

12 Benzovindiflupyr 156 Table 8 Residues of benzovindiflupyr in summer squash from field trials in Location, Application Residues, mg/ Report; (remarks) Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr cgap: 4, PHI: 0d Alton, NY (Superpik F1) Chula, GA (Dixie) Hobe Sound, FL (Fortune) York, NE (Black Beauty Zucchini) Porterville, CA (Black Beauty) a EC 100g/L; b WG 45g/L WG b 4 WG b 4 WG b Summer Squash 89 Summer Squash 75 Summer Squash 76 Summer Squash 89 Summer Squash DALA: days after last treatment Analytical method: GRM042.03A, Benzovindiflupyr. Mean = 103%, RSD = ±12% (n = 16 in 0.01 mg/) , (0.022) , 0.022, (0.022) , 0.021, (0.021) , 0.072, (0.049) , 0.035, () , 0.018, (0.017) 0 0, 0.017, () , (0.019) TK TK TK TK TK TK TK TK TK TK Table 9 Residues of benzovindiflupyr in cantaloupe from field trials in Location, Application Residues, mg/ Report; (remarks) Year (variety) Form. no cgap: 4, PHI: 0d Chula, GA (Athena) BBCH Sample DALA Benzovindiflupyr 89 Cantaloupe , 0.046, (0.048) TK TK

13 157 Benzovindiflupyr Location, Application Residues, mg/ Report; (remarks) Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr cgap: 4, PHI: 0d WG b , 0.045, (0.053) Rice, MN (Honey Rock) 76 Cantaloupe , 0.12, 0.16 (0.14) TK TK WG b , 0.090, (0.097) Wall, TX (Jumbo Hales Best) Cantaloupe , (0.049) TK TK Porterville, CA (Hales Best Jumbo) WG b Cantaloupe , 0.033, (0.026) , 0.031, (0.019) TK TK Paso Robles, CA (Top Mark) Cantaloupe 0 0, 0 (0) TK TK Sanger, CA (Oro Rico) Cantaloupe , (0.12) TK TK a EC 100g/L; b WG 45g/L DALA: days after last treatment Analytical method: GRM042.03A, Benzovindiflupyr. Mean = 105%, RSD = ± 13%, (n = 8 in mg/)

14 Benzovindiflupyr 158 Table 10 Residues of benzovindiflupyr in peppers from field trials in Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks)* cgap: 4, PHI: 0d Athens, GA (Yolo) Winter Garden, FL (Patriot) Stafford, KS (Better Belle) WG b 4 WG b Bell - Pepper 79 Bell - Pepper 87 Bell - Pepper 87 Bell - Pepper 73 [08/15/2011] Bell - Pepper ,, (0.093) ,0.11,0.071 (0.089) ,0.62 (0.62) ,0.51,0.48 (0.54) ,0.033 () TK TK TK TK Two different brands of crop oil concentrate adjuvants were used. TK TK Wall, TX (Camelot) Bell - Pepper ,0.062 (0.059) TK TK Arroyo Grande, CA (Crusader) WG b Bell - Pepper 89 Bell - Pepper ,0.085,0.12 () ,0.095,0.082 (0.096) TK TK Sanger, CA (Grande Rio) Bell - Pepper 1 (0.36) TK TK Larned, KS (Tam Hot Jalapeno) 74 Non- Bell Pepper ,0.043 (0.054) TK TK Wall, TX (Grande Jumbo Hybrid, Jalapeno) [08/11/2011] Non- Bell Pepper , ,0.055 (0.061) TK TK

15 159 Benzovindiflupyr Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks)* cgap: 4, PHI: 0d Corning, CA (Lamuyo #943) Non- Bell Pepper ,0.32 (0.35) TK TK a EC 100g/L b WG 45g/L DALA: days after last treatment * Analytical Method: GRM042.04A, Benzovindiflupyr. Bell-Pepper: Mean = 92% RSD = ± 14% (n = 12 in mg/) Non-Bell Pepper: Mean = 75%, RSD = ± 4.7% (n = 4 in mg/) Table 11 Residues of benzovindiflupyr in tomatoes from field trials in Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks)* cgap: 4, PHI: 0d Alton, NY (POLBIG F1) 86 Tomato 0, () TK TK Jeffersonville, GA (Red Bounty) WG b Tomato ,0.045,0.064 (0.053) 85 Tomato 0,0.045,0.039 (0.049) TK TK Winter Garden, (Large Cherry) 84 Tomato , 0.46 (0.43) TK TK Hobe Sound, FL (FL47) Tomato 0, () TK TK Rice, MN (Arkansas Traveler) WG b Tomato ,0.024,0.070 (0.047) 73 Tomato ,0.043,0.065 (0.061) TK TK Porterville, CA (Roma VF) Tomato ,,0.27 (0.14) TK TK

16 Benzovindiflupyr 160 Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks)* cgap: 4, PHI: 0d WG b Tomato ,0.086, (0.12) Paso Robles, CA (Galilea, Roma) 86 Tomato ,0.071 (0.085) TK TK Kerman, CA (Roma) 85 Tomato , 0.18 (0.18) 0.15,0.25 (0.20) TK TK Visalia, CA (Romas) Tomato , (0.086) 0.11,0.11 (0.11) TK TK Sanger, CA (Quality 27) [08/17/2011] Tomato TK TK Sanger, CA (Shasta) [11/01/2011] Tomato ,0.36 (0.38) TK TK Sanger, CA (Shasta) EC a (5X) Tomato 0 2.1,1.6 TK TK Kettleman City CA (8004) 89 Tomato ,0.036 (0.044) TK TK Kettleman City CA (8004) EC a (5X) Tomato , 0.24 TK TK a EC 100g/L b WG 45g/L DALA: days after last treatment * Analytical Method: GRM042.04A. Benzovindiflupyr. Mean = 95%, RSD = ± 9.0% (n = 16 in mg/)

17 161 Benzovindiflupyr Table 12 Residues of benzovindiflupyr in sweet corn (Ears) from field trials in Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks)* cgap: Canada, 2, PHI: 7d Germansville, PA (Extra Tender 274A) North Rose, NY (Serendipity) Athens, GA (Silver King) Ears 7, () 75 Ears 7, () 73 Ears 7, () TK E Ears 7.2 TK E Ears 6.0 TK E Ears 7.1 Oviedo, FL (Silver Queen) Ears 7, () TK E Ears 8.7 Gardner, ND (Zea Mays GH4927) 75 Ears 7, () TK C Ears 6.4 Bagley, IA (Not listed) Ears 7, () TK C Ears 6.7 Oregon, MO (Bodacious) Ears 7, () TK C Ears 7.3 Centerville, SD (Kandy Korn) Ears 7, () TK C Ears 6.5 Clarence, MO (Incredible) 85 Ears 7, () TK C Ears 7.2 Porterville, CA (Bodacious) Ears 7, () TK W Ears

18 Benzovindiflupyr 162 Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks)* cgap: Canada, 2, PHI: 7d Rupert, ID (Sugarbuns) Ears 7, () TK W Ears 6.9 Hillsboro, OR (Honey and Pearls) Ears 7, () TK W Ears 6.0 Wall, TX (Hybrid 111RM GT/CB/LL/RW) WG 4 7 days prior to milk stage Ears 7,,, () Bagley, IA (111RM) EC 4 7 days prior to milk stage Ears 7,,, () Rice, MN (DKC 35-43) EC 4 7 days prior to milk stage Ears 7,,, () a EC 150g/L DALA: days after last treatment *Analytical Method: GRM042.03A. Benzovindiflupyr, Sweet Corn Ears: Mean = 88%, RSD = ± 12% (n = 6 in mg/) Table 13 Residues of benzovindiflupyr in pulses (peas and beans) in Canada and the (Seed) Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks) GAP: Canada, 2, PHI: 15d Hinton, OK, (Alaska) Dried Pea Seed ,, ( ) 0.11 TK TK months WG a Dried Pea Seed 14, 0.023, () TK TK months American Falls, ID, (Little Marvel) WG a Dried Pea Seed Dried Pea Seed ,, (0.016) 14,, (0.017) TK TK months TK TK months Jerome, Dried 0 TK

19 163 Benzovindiflupyr Location, Application Residues, mg/ Report; Year (variety) Form. no GAP: Canada, 2, PHI: 15d ID, (SNO N14) BBCH Sample DALA Benzovindiflupyr (remarks) Pea Seed , () TK months Hillsboro, OR, (Blue Bird) Madera, CA, (Dundale) Clarence, MO, 2011 (HMS Medalist)) Perley, ND (Navigator) York, NE, (Marquis- GT) Campbell, MN, (HMS Medalist) Gardner, ND, (Maverick) WG a 2 WG a 2 WG a Dried Pea Seed Dried Pea Seed Dried Pea Seed R8/95 Bean Seed R8/95 Bean Seed Dried Beans Seed Dried Beans Seed Beans Seed Beans Seed Dried Beans Seed 14, () 14,, () , 0.017, (0.028) 14,, () 14,, (0.011) 14,, () 14,, () 14, (0.044) 14, () , () TK TTK months TK TK months TK TK months TK TK months TK TK months TK TK months TK TK months TK TK months TK TK months TK TK months( 14DALA)

20 Benzovindiflupyr 164 Location, Application Residues, mg/ Report; Year (variety) Form. no GAP: Canada, 2, PHI: 15d Hinton, OK, (Dwarf Horticulture Taylor Bean) WG a BBCH Sample DALA Benzovindiflupyr (remarks) Dried Beans Seed Dried Beans Seed 14,, (0.010) 14,, () TK TK months TK TK months Wall, TX, (Pinto III) Dried Beans Seed 14, () TK TK months Madera, CA, (UC-8537) Dried Beans Seed , (0.045) TK TK months American Falls, ID, (Pinto) Dried Beans Seed , (0.020) TK TK months Canada St-Marc-Sur- Richelieu, QC, (Hooter) [Aug 11,2012] Dried Beans Seed , (0.011) 0.01 CER05904/11 T months Canada St-Marc-Sur- Richelieu, QC, (Etna) WG b [Aug 11,2012] [Aug 11,2012] Dried Beans Seed Dried Beans Seed 14, () 14, () CER05904/11 T months CER05904/11 T months Canada Vanscoy, SK, (AC Pintoba) Dried Beans Seed , () CER05904/11 T months WG b Dried Beans Seed , (0.23) CER05904/11 T months Canada Taber, AB, (Great Northern) WG b Dried Beans Seed Dried Beans , (0.010) , (0.016) CER05904/11 T months CER05904/11 T953

21 165 Benzovindiflupyr Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks) GAP: Canada, 2, PHI: 15d Seed months Canada Minto, MB, (Pintabo) Dried Beans Seed 16, () CER05904/11 T months Canada Vanscoy, SK, (CDC Bronco) Dried Pea Seed 15, (0.049) CER05905/11 T months WG b Dried Pea Seed , (0.034) CER05904/11 T months Canada Perdue, SK. (CDC Bronco) Dried Pea Seed , (0.033) CER05905/11 T months Canada Minto, MB. (CDC Golden) Dried Pea Seed , (0.011) CER05905/11 T months Canada Boissevain, MB, (CDC Meadow) WG b Dried Pea Seed Dried Pea Seed 16, () 16, () CER05905/11 T months CER05905/11 T months Canada Rosthern, SK 2011 ( Meadow) Dried Pea Seed 16, () Report: CER05905/11 T months WG b Dried Pea Seed 16, () CER05905/11 T months a EC 100 g/l; WG 45 g/l b WG 150 g ai/l Analytical Method: GRM042.04A, Benzovindiflupyr, LOQ: 0.01 mg/ Pea and bean seeds Mean = 112%,RSD = ± 6.9%,(n = 6 in mg/)

22 Benzovindiflupyr 166 Table 14 Residues of benzovindiflupyr in soya bean in the (seed) Location, Application Residues, mg/ Report; Year (variety) Form. no GAP: Canada, 2, PHI: 14d, Soya beans BBCH Sample DALA Benzovindiflupyr (remarks) Elko, SC, (Asgrow 7502) Seven Springs, NC, (AG5605) Cheneyville, LA, (Pioneer 94M80) Cheneyville, LA, (Asgrow 5335) Pollard, AR, (Pioneer 94M80) Northwood, ND, (90Y41) Sharon, ND, (90Y41) Gardner, ND, ( ) Dudley, MO, (Asgrow Seed 14, () [09/01/2010] [10/04/2010] Seed 14, () Seed 14, () Seed 14, () Seed 14, () Seed , () Seed 14, () Seed 14, (0.018) Seed , (0.069) Seed 14, () E months E months E months E months C months C months C months C months C months; 5X for processing study C months

23 167 Benzovindiflupyr Location, Application Residues, mg/ Report; Year (variety) Form. no GAP: Canada, 2, PHI: 14d, Soya beans BBCH Sample DALA Benzovindiflupyr (remarks) 5403) Fisk, MO, (Jake) Seed 14, () C months Fitchburg, WI, (S21-N6) Bagley, IA, (P3Y13- N203) Oregon, MO, (Pioneer 93Y70) York, NE, (93Y12) Lesterville, SD, (Latham, L2560R, LS ) Marysville, OH, (SG-329- RR) R6-R Seed 14, () Seed 14, () Seed , (0.012) Seed 14, () Seed 14,.017,,0.012,, (0.012) Seed 14, () Seed 14, () C months C months C months C months C months C months C months Clarence, MO, (Asgrow 3803 RR) R7 Seed ,0.011 (0.011) C months (14DALA) Richland, IA, Seed 14, (0.064) C months

24 Benzovindiflupyr 168 Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks) GAP: Canada, 2, PHI: 14d, Soya beans (Pioneer 92Y80) Campbell, MN, (AG 0808) 93 Seed 14, () C months Geneva, MN, (Pioneer 91Y70) Seed 14, () C months a EC 150 g ai/l Analytical Method: GRM042.04A, Benzovindiflupyr, LOQ: 0.01 mg/ soya bean: Mean = 94%, SD = ± 14%,(n = 16 in mg/) Table 15 Residues of benzovindiflupyr in potato from field trials in Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks)* cgap: 4, PHI: 14d Alton, NY (Reba) WG b 4 47 Potato 14 0, 0, 0 (0) 47 Potato 14 0, 0, 0 (0) TK ; TK North Rose, NY (Genesee) Potato 14 0, 0 (0) TK ; TK Jeffersonville,GA (Red Pontiac) Potato 14 0, 0, 0 (0) 93 Potato 14 0, 0 (0) TK ; TK Oviedo, FL (Red Potato 14 0, 0 (0) TK ; TK

25 169 Benzovindiflupyr Location, Application Residues, mg/ Report; Year (variety) Form. no cgap: 4, PHI: 14d LaSoda) Oregon, MO (Red Pontiac) York, NE (Russet Norkotah) Bagley, IA (Kennebec) Oregon, MO (Yukon Gold) Jerome, ID (Ranger Russet) Sanger, CA (Red La Soda) American Falls, ID (Russet Burbank) American Falls,ID (Dark Red Norland) WG b 4 WG b BBCH Sample DALA Benzovindiflupyr (remarks)* 49 [08/18/2011] Potato ,0.017 (0.014) 75 Potato 14 0, 0.010, 0 (0.010) 75 Potato 14 0, 0, (0.010) 75 Potato 14 0, 0 (0) 75 Potato 14 0, 0 (0) 93 [08/04/2011] Potato , (0.012) 47 Potato 14, () 46 Potato 14, () 47 Potato ,, (0.011) 47 [09/13/2011] 49 [08/30/2011] Potato , 0.012, (0.014) Potato 14 0, 0 (0) TK ; TK TK ; TK TK ; TK TK ; TK TK ; TK TK ; TK TK ; TK TK ; TK American Potato 14 0, 0 TK ;

26 Benzovindiflupyr 170 Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks)* cgap: 4, PHI: 14d Falls,ID (Norkotah) [09/06/2011] Potato , 0 (0.011) (0) TK Ephrata,WA (Umatilla) 47 Potato 14 0, 0 (0) TK ; TK Rupert, ID (Russet Burbank) [08/31/2011] Potato , TK ; TK Rupert, ID (Russett Burbank) [08/31/2011] Potato 14 0, 0 (0) TK ; TK a EC 100g/L b WG 45g/L DALA: days after last treatment * Analytical Method: GRM042.03A, Benzovindiflupyr. Mean = 100%, RSD = ± 9.5% (n = 16 in mg/ spiking range) Table 16 Residues of benzovindiflupyr in barley (grain) from field trials in the Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks)* cgap: 2, PHI: maturity Germansville, PA (Nomini) BBCH 71 (Grain) STM 0.30,0.58,0.65,0.50,0.70,0.51 (0.54) TK ; E Northwood, ND (Pinneacle) Feekes (Grain) STM 0.013, (0.014) TK ; C Richland, IA (Paramount 66) Feekes 11.1 (Grain) STM 2.3, 3.1 (2.7) TK ; C data not used due to misapplication BBCH TK ;

27 171 Benzovindiflupyr Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks)* cgap: 2, PHI: maturity Clarence, MS (Lacey) 71 (Grain) STM 0.45, 0.54, 0.58, 0.62, 0.65, 0.70 (0.59) C Jamestown, ND (Tradition) BBCH 71 (Grain) STM 0.35, 0.30 (0.32) TK ; C Grand Island, NE (Baronesse) BBCH 71 (Grain) STM 0.26, 0.27, 0.25, 0.27, 0.24 (0.26) TK ; C Carrington, ND (Baronesse) Feekes (Grain) STM 0.028, (0.029) TK ; C Lake Andes, SD (Tradition) BBCH 73 (Grain) STM 0.29, 0.31 (0.30) TK ; C Berthoud, CO (Coors 69) Feekes (Grain) STM 0.069, (0.079) TK ; W Madera, CA (Recleaned Whole Barley) BBCH 71 (Grain)*** STM 0.089, 0.12 () TK ; W *** Residue of mg/ benzovindiflupyr in control sample. 8.9 Hermiston, OR (Radiant) BBCH 84 (Grain) STM 0.35, 0.36 (0.36) TK ; W Jerome, ID (Foster) BBCH 71 (Grain) STM 0.059, (0.061) TK ; W a EC 150g/L; DALA: days after last treatment * Analytical Method: GRM042.03A, Benzovindiflupyr. Grain: Mean = 108%, RSD = ± 9.4% (n = 12 in mg/)

28 Benzovindiflupyr 172 Table 17: Residues of benzovindiflupyr in barley (grain) from field trials in Canada Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks)* GAP: Canada, 2, PHI: maturity Taber, AB (CDC Earl) (Grain) , 0.95 (0.92) CER05902/11; T Elgin, MB (AC Metcalfe) [04-Aug- 11] (Grain) , 0.13 (0.15) CER05902/11; T Minto, MB (Copeland) [25-Jul- 11[ (Grain) , 0.11 (0.12) CER05902/11; T Elgin, MB (Tradition) [04-Aug- 11] (Grain) , 0.33 (0.29) CER05902/11; T Rosthern, SK (Metcalfe)) (Grain) , 0.12 (0.12) CER05902/11; T Duck Lake, SK (Metcalfe) (Grain) , (0.096) CER05902/11; T Fort Sask. AB (Coalition) 71 (Grain) , 0.46 (0.42) CER05902/11; T Wellwood, MB (Conlon) (Grain) , 0.19 (0.21) CER05902/11; T Minto, MB (Legacy) 73 [21-Jul- 11] (Grain) 43 (0.17) a EC 100g/L; An adjuvant named Agral 90, rate as 0.2%v/v was used in all trials. CER05902/11; T DALA: days after last treatment * Analytical Method: GRM042.03A, Benzovindiflupyr. Mean = 86%, RSD = ± 12% (n = 8 in mg//)

29 173 Benzovindiflupyr Table 18 Residues of benzovindiflupyr in maize (grain and Popcorn Grain) from field trials in Location, Application Residues, mg/ Report; Year (variety) Form. no Germansville, PA (TA ) Athens, GA (32B10) cgap: Canada, 2, PHI: 7 d BBCH Sample DALA Benzovindiflupyr (remarks)* 89 grain 7, ( ) 88 grain 7, ( ) E E Gardner, ND (Int65D85R) Northwood, ND (DKC35-19/ A ) Fisk, MO (RL8950HB) Oregon, MO (Pioneer 32T16) Fitchburg, WI (37Y12) grain , ( 0.014) 89 grain , ( 0.017) 95 grain 7, ( ) 89 grain 7, ( ) 96 grain 7, ( 0.010) C C C C C Bagley, IA (33D47) Bolckow, MO (Mycogen2 K718) Sharon, ND (DKC35-19/ A ) grain [10/09/2010] 7, ( ) 89 grain 7, ( ) 89 grain , ( ) C C C

30 Benzovindiflupyr 174 Location, Application Residues, mg/ Report; Year (variety) Form. no Lesterville, SD (Golden Harvest H GT, var. 162X579 14WP917) cgap: Canada, 2, PHI: 7 d BBCH Sample DALA Benzovindiflupyr (remarks)* 92 grain 7, ( ) C Richwood, OH (DKC57-66 VT3/RR2) grain 7, ( ) C Clarence, MO (Pioneer 33D49) Osceola, NE (4947RB) grain 7, ( ) 89 grain 7, ( ) C C Campbell, MN (DKC 38-89) 85 grain 7, ( ) C Geneva, MN (Pioneer 38M60) Perry, IA (P1162XR) York, NE (X723 14WP.0) grain 7, ( 0.014) 97 grain 7, ( ) 89 grain 7, ( 0.014) C C C

31 175 Benzovindiflupyr Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks)* Anabel, MO (33T57) Raymondville, TX (HG284162) Levelland, TX (AP2504, Popcorn) cgap: Canada, 2, PHI: 7 d grain 7, ( ) 87 Grain 7, ( ) 99 Grain 7, ( ) C W W Wall, TX (Hybrid 111RM GT/CB/LL/RW) WG b 4 99 Grain 7, ( ) 71 Grain 7, ( ) Bagley, IA (111RM) 99 [10/09/2010] Grain 7, ( ) WG b Grain 7, ( ) Rice, MN (DKC 35-43) a EC 150g/L b WG 45g/L WG b 4 99 Grain 7, ( ) 73 Grain 7, ( ) DALA: days after last treatment * Analytical Method: GRM042.03A, Benzovindiflupyr Field Corn Grain: Mean = 89%, RSD = ± 12% (n = 12 in mg/)

32 Benzovindiflupyr 176 Table 19 Residues of benzovindiflupyr in wheat (grain) from field trials in Location, Application Residues, mg/ Report; (remarks) c Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr Seven Springs, NC (Pioneer 26R15) Fisk, MO (Beretta) Northwood, ND (Jerry) Shelbyville, MO (Erine) Richland, IA (Wilcross748) Milford Center, OH (Croplan Genetics 8614) Macon, MO (V9710) Raymondville, TX (Caudillo) cgap: Canada, 2, PHI: Maturity Feekes Feekes Feekes Feekes Feekes Grain STM 0.037,0.044 () 73 Grain STM 0.069,0.013 () Feekes Grain STM,,*,* () Grain STM, () Grain STM 0.025, (0.035) Grain STM,,*,* (0.046) Grain STM, () Grain STM 0.022,0.018 (0.020) E C C C C C C W Carrington, ND (AP-604-CL) Feekes Grain STM, () C

33 177 Benzovindiflupyr Location, Application Residues, mg/ Report; (remarks) c Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr Jamestown, ND (Not known) cgap: Canada, 2, PHI: Maturity Grain 7 DBSM STM 7 DASM , (0.016) C DASM Grain 7 DBSM STM 7 DASM 14 DASM * * * *, * (*) C Carrington, ND (Faller) Lake Andes, SD (Argent) Grand Island, NE (NEO1643) Johnstown, CO (Yuma) Eaton, CO (Jalgalene) Feekes Feekes Feekes 10.5 Grain STM,,*, * () 73 Grain STM 0.026,0.012,* (0.019) 71 Grain STM 0.014,,*,* () Grain STM 0.046,0.087 (0.067) Grain 7 DBSM STM 7 DASM ,0.023 C C C W W DASM Uvalde, TX (Tam 203) Grain STM, () W

34 Benzovindiflupyr 178 Location, Application Residues, mg/ Report; (remarks) c Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr Wall, TX (Coronado) Levelland, TX (Weather master) Milliken, CO (Bill Brown) Rupert, ID (Klassic) Valley City, ND (Falcon) cgap: Canada, 2, PHI: Maturity WG b Feekes Grain STM 0.012,0.012 (0.012) Grain STM 0.042, (0.059) Feekes Grain STM 0.086,0.060 (0.072) 71 Grain STM, () 73 Grain SM 0.026,0.017,0.019 (0.021) 73 Grain SM 0.024,0.025,0.020 (0.023) W W W W TK TK Jamestown, ND (Overland) Grain SM 0.024,0.021, () WG b Grain SM,0.010, (0.016) TK TK Northwood, ND (Faller) a EC 150g/L b WG 45g/L WG b 2 71 Grain SM,, () 71 Grain SM,, () TK TK DALA: days after last treatment *Trt 2 grain and straw data was from selected trials requested from Syngenta Canada to evaluate residues from early application to normal harvest. c Analytical Method: GRM042.03A, Benzovindiflupyr. Grain: Mean = 95%, RSD = ± 8.2% (n = 4 in mg/)

35 179 Benzovindiflupyr Table 20 Residues of benzovindiflupyr in wheat (grain) from field trials in Canada Location, Application Residues, mg/ Report; Year (variety) Vanscoy, SK (Infinity)) Form. no cgap: Canada, 2, PHI: Maturity BBCH Sample DALA Benzovindiflupyr (remarks) b 59 Grain , (0.031) CER05901/11; T Kinley, SK (Infinity) Grain ,0.036 (0.042) CER05901/11; T Taber, AB (Superb) Grain 32, () CER05901/11; T Boissevain, MB (Harvest) Grain , (0.026) CER05901/11; T Boissevain, MB (Kane) Rosthern, Sk (Infinity) Grain 43, (0.012) 71 Grain 52, (0.011) CER05901/11; T CER05901/11; T Blaine Lake, SK (Infinity) Duck Lake, SK (Infinity) Grain 54, () 71 Grain ,0.037 (0.032) CER05901/11; T CER05901/11; T

36 Benzovindiflupyr 180 Location, Application Residues, mg/ Report; Year (variety) Kipp, AB (Superb) Form. no cgap: Canada, 2, PHI: Maturity BBCH Sample DALA Benzovindiflupyr (remarks) b 71 Grain , (0.017) CER05901/11; T Alvena, SK (Goodeve Ac Intrepid) Grain ,0.025* (0.025) CER05901/11; T Fort Sask. AB, (Harvest) Grain 44, (0.025) CER05901/11; T Minto, MB (Superb) Minto, MB (AC Barrie) Grain ,0.022 (0.023) 71 Grain 35,0.012 (0.026) CER05901/11; T CER05901/11; T a EC 150g/L; DALA: days after last treatment b Analytical Method: GRM042.03A, Benzovindiflupyr. Grain: Mean = 95%, RSD = ± 8.2% (n = 4 in mg/) Table 21 Residues of benzovindiflupyr in sugar cane from field trials in Brazil Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks) cgap: Brazil, , PHI: 30d Mirassol, (SP ) EC a 5 (30) 42 Sugarcane Jaboticabal, WG b 5 (30) EC a 5 (30) 42 Sugarcane Sugarcane M11013 M11013-AMA1 5 M11019 M11019-AMA1 5 M11013 M11013-AMA2

37 181 Benzovindiflupyr Location, Application Residues, mg/ Report; Year (variety) Form. no BBCH Sample DALA Benzovindiflupyr (remarks) cgap: Brazil, , PHI: 30d (RB 5453) 40 5 Jaboticabal, (SP ) Bandeirantes, (RB 72454) Tupaciguara, (SP 86155) Rio das Pedras, (RB ) WG b 5 (30) (A17961) 5 EC a (30) (A17961) EC a 5 (30) EC a 5 (30) WG b 5 (30) EC a 5 (30) WG b 5 (30) EC a 5 (30) WG b 5 (30) (A17961) 5 EC a (30) (A17961) EC a 5 (30) EC a 5 (30) Sugarcane Sugarcane Sugarcane Sugarcane Sugarcane Sugarcane Sugarcane Sugarcane Sugarcane Sugarcane , () 0.07, 0.01 (scaled from proportionality 0.01) (0.02) 0.03, 0.01 (0.02) 0.05, 0.01 (0.04) Scaled mean:0.014 M11019 M11019-AMA2 5 M11007 M11007-AMA2 5 M11013 M11013-DMO 5 M11019 M11019-DMO 5 M11013 M11013-JJB 5 M11019 M11019-JJB 5 M11013 M RWC1 5 M11019 M RWC1 5 M11007 M RWC2 5 M11013 M RWC2