First draft prepared by Dr Ursula Banasiak, Federal Institute for Risk Assessment, Berlin, Germany

Transcription

1 403 THIOPHANATE-METHYL (077) First draft prepared by Dr Ursula Banasiak, Federal Institute f Risk Assessment, Berlin, Germany EXPLANATION Thiophanate-methyl and its related compounds benomyl and carbendazim were evaluated by the 998 JMPR as part of the CCPR Periodic Review Programme. The Meeting estimated MRLs (expressed as carbendazim) f beans (dry), garden peas (succulent seeds), grapes, pome fruits and wheat on the basis of thiophanate-methyl residue data. At the 34 th Session of the CCPR (2002), the Committee recommended the deletion of all CXLs f thiophanate-methyl as the cresponding proposed MRLs f carbendazim (072) had reached Step 8. The Committee agreed to change the JMPR residue definition sum of thiophanate-methyl and carbendazim, expressed as carbendazim to sum of benomyl, carbendazim and thiophanate-methyl, expressed as carbendazim. The 2003 JMPR received infmation on GAP and national MRLs from the governments of Germany (Anonymous, 2003) and the Netherlands (Muller, 2003). The manufacturer submitted US GAP data (labels), analytical methods, infmation on stability of residues in sted analytical samples and new US supervised residue trial data on cherries, summer squash, snap beans, soya beans, sugar beet roots and tops, peanut nutmeat and hay. METHODS OF RESIDUE ANALYSIS Analytical methods The Meeting received infmation on two analytical methods used in the determination of residues. In one method, f the determination of thiophanate-methyl, carbendazim, DX-05 2 and FH-432 3, the analytes are extracted with acidic methanol, purified by liquid-liquid partition and analyzed by columnswitching HPLC with two reversed phase columns and UV detection. Thiophanate-methyl and DX-05 were determined in one injection by switching the effluent from the first column from waste to the second analytical column at the appropriate retention window and measuring the absbance at 235 nm. Carbendazim and FH-432 were determined similarly in a separate injection using a different retention window and a wavelength of 280 nm f carbendazim and 235 nm f FH-432. The LOQ is 0.05 mg/kg f each analyte. The mean and standard deviation of recoveries f thiophanate-methyl from snap bean, soybean seed, cherries, peanut nutmeat and peanut hay were 90±5%, 99±8%, 89±7%, 86±6% and 88±8%, respectively. Those f carbendazim were 84±3%, 90±5%, 79±0 %, 89±9% and 89±0%, respectively (Williams, 995, 996, 998; Burton, 998). In the second method, f the determination of thiophanate-methyl and carbendazim, the analytes are extracted with acidic methanol, purified by solid-phase extraction on C-8 cartridges and analysed by column-switching HPLC with two reverse phase columns and UV detection by photodiode array (PDA). The wavelength selected f analysis of each compound may vary accding matrix interferences experienced with the final sample extract at the anticipated retention time of the analyte. The LOQ is 0.05 mg/kg f each analyte. The mean and standard deviation of recoveries f thiophanate-methyl from This evaluation was perfmed f the 2003 meeting of JMPR. It is a crigendum to Pesticide residues in food Evaluations Part I Residues. Appraisal, recommendations and dietary risk assessment f carbendazime and yhiophanate-methyl were already published in said document (pp 23-3). 2 Methyl-N-[2-(N -methoxycarbonyl-thioureido)phenylaminocarbonyl]carbamate 3 Allophanate, dimethyl[(,2-phenylene)bis(iminocarbonyl)]bis(carbamate)

2 404 thiophanate-methyl sugar beet roots and tops were 83±2% and 73±20%. Those f carbendazim were 8±8% and 83±9% (Carr, 998). The range of recoveries f thiophanate-methyl and carbendazim from summer squash was 56-97% and 57-38%, respectively (Carr, 997, 998). Stability of pesticide residues in sted analytical samples Stability data of thiophanate-methyl residues in soya bean seed, snap bean and sugar beets after stage f 4-5 years were submitted. The residue remaining of thiophanate-methyl in soybean seed after 5-year stage was 88-93% of the initial level (Chickering, 2003). With regard to snap bean and sugar beets, the residue remaining after 4-year stage in relation to the initial level was 77-86% and 00-06%, respectively (Whitsel, 200a, 200b). Freezer stability of carbendazim was assessed over 24 months in snap beans, apples, spinach, sugar beet roots, wheat grain, and tomatoes. The residue remaining of carbendazim in the investigated crop matrices after 24-month stage was me than 80% of the initial level (Hundley, 996). USE PATTERN Infmation on registered uses was repted to the Meeting and is shown in Table. Labels were submitted f USA GAP. The Meeting was infmed that the compound is no longer registered in Germany. Table : Registered uses of thiophanate-methyl spraying, post-harvest treatment and soil drenching. Crop Country ulation Method Rate kg ai/ha Spray conc. kg ai/hl Almonds USA WP 700 g/kg, red bud stage and to petal WSB ) 700 g/kg fall Apple Netherlands WP 700 g/kg, pre-blossom Apple Netherlands WP 700 g/kg, during blossom Apple Netherlands WP 700 g/kg, 6 and 2 weeks befe harvest Apple Netherlands WP 700 g/kg, post harvest flood spray treatment Apple Netherlands WP 700 g/kg,, st 0-20% leaf fall, 2 nd 80-90% leaf fall Apple USA WP 700 g/kg Apricot USA WP 700 g/kg, Beans USA WP 700 g/kg, (except CA) Beans Canola USA (CA only) USA (ND, MI, MO only) WP 700 g/kg, at the end of leaf fall, interval 5-4 days, from green tip to petal fall, interval 0-4 days, interval minimum 7 days, maximum 3. kg ai/ha per year, at 50-70% of full bloom st 0-30% of full blooming, 2 nd 4-7 days later at peak bloom, 20-50% of blooming 20-30% and 40-50% of blooming, maximum.6 kg ai/ha No as, days as snap and lima beans, 28 dry beans 4 snap and dry beans, 28 lima beans

3 thiophanate-methyl 405 Crop Country ulation Method Rate kg ai/ha Spray conc. kg ai/hl per year Cherries USA WP 700 g/kg,, interval 0-4 days Cucumber USA WP 700 g/kg, ground treatment aerial, interval 7-4 days, WSB: maximum 2.2 kg ai/ha per year as Courgette Netherlands WP 700 g/kg,, interval 0-4 days G Dwarf beans Netherlands WP 700 g/kg,, 3 days befe top (dry) blossoming, interval 5-7 days Eggplant Netherlands WP 700 g/kg,, interval 0-4 days G Garlic USA Dipping befe planting Grapes USA, interval 4 days, maximum 3. kg ai/ha per year Leek Netherlands WP 700 g/kg, dipping befe planting Melons Netherlands WP 700 g/kg,, interval 0-4 days G Melons Netherlands WP 70 soil drench after planting 0.7 g ai per plant -3 3 G Melons USA WP 700 g/kg, ground treatment aerial, interval 7-4 days, WSB: maximum 2.2 kg ai/ha per year as Mushrooms Netherlands WP 700 g/kg surface drench of bed, after casing G Mushrooms Netherlands WP 700 g/kg f mechanically harvested champignons: spraying of aerial parts immediately after harvest of the st and 2 nd flush G Nectarine USA WP 700 g/kg,, interval 0-4 days Onion Netherlands WP 700 g/kg, seed treatment Onion Netherlands WP 700 g/kg, Onion USA WP 700 g/kg in furrow at planting plant onion and shallots: dipping befe planting 0.4 kg ai/ 00 kg seed No g/m as as Peanut USA WP 700 g/kg,, after planting, interval 4-2 days (WP), 7-4 days (WSB) 4 Peach USA WP 700 g/kg,, interval 0-4 days Pear Netherlands WP 700 g/kg, pre-blossom Pear Netherlands WP 700 g/kg, 6 and 2 weeks befe harvest Pear Netherlands WP 700 g/kg, post harvest shower treatment Pear Netherlands WP 700 g/kg, , st 0-20% leaf fall, 2 nd 80-90% leaf fall at the end of leaf fall Pear USA, interval 5-0 days, as maximum 3. kg ai/ha per year Pecan USA WP 700 g/kg,, interval 3-4 weeks, as aerial treatment in GA, AR, LA, MS, OK, TX only Pistachio USA ground aerial treatment as, days

4 406 thiophanate-methyl Crop Country ulation Method Rate kg ai/ha Spray conc. kg ai/hl nut maximum.6 kg ai/ha per year Plums USA WP 700 g/kg,, interval 0-4 days as Potato, seed Netherlands WP 700 g/kg, post harvest use, kg ai/ spraying of potatoes, not f 00 kg seed Potato, seed Netherlands 350 g/l Potato USA (except CA) Pumpkin USA WP 700 g/kg Soya bean USA WP 700 g/kg, Squash, summer USA WP 700 g/kg, Strawberry USA WP 700 g/kg, Sugar beet USA WP 700 g/kg consumption animal feed post harvest use, spraying of potatoes, not f consumption animal feed, interval 7-4 days, maximum 3. kg ai/ha per year ground treatment aerial, interval 7-4 days, WSB: maximum 2.2 kg ai/ha per year, interval 4-2 days; do not graze feed treated vines hay to livestock ground treatment aerial, interval 7-4 days, WSB: maximum 2.2 kg ai/ha per year Tomato Netherlands WP 700 g/kg, Triticale USA (ID, ground aerial treatment, OR, WA after tillering only) Watermelon USA ground treatment aerial, interval 7-4 days, WSB: maximum 2.2 kg ai/ha per year Wheat Netherlands WP 700 g/kg, Wheat USA WP 700 g/kg, (fall seeded) (ID, OR, WA only) ) WSB: 70% wettable powder in water soluble bags kg ai/ 00 kg seed No as as as, days, interval 7-0 days, maximum 3. kg ai/ha per year as, interval 4-2 days; 0.39 as 2 maximum 2.4 kg ai/ha per year G hay as, at crop height of 25 cm ground aerial treatment, after tillering RESIDUES RESULTING FROM SUPERVISED TRIALS ON CROPS The Meeting received infmation on supervised field trials f the following crops. Fruits Table 2 Cherries Vegetables Table 3 Summer squash Table 4 Snap beans Table 5 Soya bean Table 6 Sugar beet root Oilseed Table 7 Peanut Feed commodities Table 8 Snap bean vines Table 9 Soya bean hay Table 0 Peanut hay Table Sugar beet tops 0.78 hay 90

5 thiophanate-methyl 407 The residue trials were well documented with full labaty and field repts. Labaty repts included method validation. Dates of analyses were also provided. Periods of freezer stage between sampling and analysis were recded f all trials and were within the acceptable determined stability period. Field repts provided data on the sprayers used and their calibration, plot size, residue sample size and sampling dates. Where residues were not detected, data are recded in the Tables as below the LOQ. Residue data, application rates and spray concentrations have generally been rounded to two significant figures, f residues near the LOQ, to one significant figure. Although trials included control plots, no control data are recded except where residues in control samples exceeded the LOQ. Residues are recded unadjusted f procedural recoveries. Double-underlined residue values are from treatments of maximum GAP and have been used f the estimation of maximum residue levels. Thiophanate-methyl, carbendazim, FH-432 and DX-05 were determined by the methods used. Because FH-432 and DX-05 are not included into the residue definition, only thiophanate-methyl (TM) and carbendazim (MBC) residues were repted in the Tables (as TM and MBC). The total residues are sum of thiophanate-methyl and carbendazim, calculated as carbendazim. Table 2. Thiophanate-methyl residues in cherries from supervised trials in the USA (Leppert and Castro, 996), Rept RD-II In general, results f fruits without stones, except 0-day samples of trials 23C-9 and 23D-9 f fruits with stones. Variety Montmency: sour cherry; Lambert: sweet cherry; Bada sweet: sweet cherry. location, variety 23A-92, 996, MI, Conklin, Montmency ) 23B-9, 996, MI, Conklin, Montmency 23F-9, 996, WA, White Salmon, Lambert 2) 23E-9,996, WA, White Salmon, Lambert 23C-9, 996, NY, Sodus, Montmency ) 23D-9, 996, NY, Sodus, Montmency ) 23G-9, 996, OR, Cnelius, Bada sweet 2) 23H-9, 996, OR, Gaston, Montmency 2) Method kg ai/ha kg ai/hl No. WP Ground Aerial WP Ground Aerial Ground Ground Ground Ground , days TM MBC Total as MBC ) treatment using airblast sprayers 2) Statement by the manufacturer: equipment (single nozzle chard gun) did not simulate commercial practices

6 408 thiophanate-methyl : Water Dispersible Granule Table 3. Thiophanate-methyl residues in summer squash from supervised trials in the USA (Carr, 997), Rept RD-II location, variety 27A-9, 99, CA, Fresno, Ambassad 27B-9, 99, CA, Madera, Ambassad 27G-9, 99, NC, Gaston, Golden Summer Crookneck 27C-9, 99, FL, Jupiter, Goldie 27E-9, 99, GA, Winterville, Yellow Crookneck 27H-9, 99, NY, Phelps, President 27D-9, 99, FL, Luxahatchee, Dixie 27F-9, 99, MI, Conklin, Lemondrop L 27I-9, 99, OR, Hillsbo, Elete 27J-9, 99, TX, Donna, Early Profile Straighthneck, WP Ground WP Aerial WP Ground Aerial <0.08 Ground Ground Ground Ground <0.08 Ground Ground Table 4. Thiophanate-methyl residues in snap beans from supervised trials in the USA (Leppert, 996), Rept RD-II location, variety 08A-90, 990, FL, Loxahatchee, Triumph 08B-90, 990, MN, Theilman, Hystle 08C-90, 990, MI, Marcellus, Tendercrop 08D-90, 999, NJ, Bridgeton, Provider 08E-90, 990, NY, Sodus, Tendergreen, Aerial <0.08 Ground <0.08 Ground <0.08 Ground Aerial

7 thiophanate-methyl 409 location, variety 08F-90, 990, NY, Sodus, Tendergreen 08G-90, 990, OR, Hillsbo, OSU 9 08H-90, 990, PA, Nthampton, Burpee Stringless 08I-90, 990, TN, Toone, Contender 08J-90, 990, WI, Janesville, Hy-Style 08K-90, 990, WI, Delavan, Peak, Ground Ground <0.08 Ground Ground <0.08 Aerial <0.08 Ground Table 5. Thiophanate-methyl residues in soya beans (dry) from supervised trials in the USA (Castro, 998), Rept RD-II0209. location BR A,990, AR, Scott BR B, 990, BR C, 990, IA, Muscatine BR D,990, IA, Muscatine BR E, 990, IL, Carlyle BR G,990, IN, Hebron BR H,990, LA, Rosa BR I, 990, MN, Theilman BR J, 990, MO, Leonard BR K,990, MS, Hernando BR L, 990, NE, Yk BR M,990, OH, New Holland Ground <0.08 Aerial Aerial <0.08 Ground <0.08 Ground <0.08 Ground <0.08 Ground Ground <0.08 Ground <0.08 Ground <0.08 Ground <0.08 Ground <0.08

8 40 thiophanate-methyl Table 6. Thiophanate-methyl residues in sugar beet roots from supervised trials in the USA (Carr, 998), Rept RD-II location , 997, MN, Mohead , 997, ND, Nthwood WSB Seed ) + WSB Seed ) + Method kg ai/ha kg ai/hl No. days TM MBC Total as MBC ) 2 < ) <0.08 <0.08 < , 997, WSB Seed ) ) 2 <0.08 ND, Nthwood , 997, WSB Seed ) ) 2 <0.08 ND, Richland County , 997, WSB Seed ) ) 2 <0.08 MI, Conklin , 997, WSB Seed ) ) 2 <0.08 ND, Velva , 997, WSB Seed ) ) 2 <0.08 Levelland, TX , 997, WSB Seed ) ) 2 <0.08 Eaton, CO , 997, WSB Seed ) ) 2 <0.08 CA, Pterville , 997, WSB Seed ) ) 2 <0.08 Rupert, ID , 997, ID, Jerome WSB Seed ) ) 2 <0.08 ) Seed treatment 0.25 kg ai/00 kg of seed 2) Number of applications WSB: wettable powder in water soluble bags Table 7. Thiophanate-methyl residues in peanut (nut meat) from supervised trials in the USA (Bradway, 998), Rept RD-II Peanut plants were inverted 4 days after last application and dried f several days in the field. The one exception was trial J where hay and nuts were collected at the 4-day. location 0A-9, 99, AL, Grangerburg 0B-9, 99, AL, Grangerburg 0C-9, 99, 0D-9, 99, 0E-9, 99, 0F-9, 99, NC, Whitakers 0G-9, 99, NC, Whitakers 0H-9, 99, TX, Pattison < < <0.08 <0.08 <0.08 <0.08 <0.08 <0.08

9 thiophanate-methyl 4 location 0I-9, 99, TX, Pattison 0J-9, 99, VA, Empia Method kg ai/ha kg ai/hl No days TM MBC Total as MBC < <0.08 Table 8. Thiophanate-methyl residues in snap bean vines from supervised trials in the USA (Leppert, 996), Rept RD-II location, variety 08A-90, 990, FL, Loxahatchee Triumph 08B-90, 990, MN, Theilman, Hystle 08C-90, 990, MI, Marcellus, Tendercrop 08D-90, 990, NJ, Bridgeton, Provider 08E-90, 990, NY, Sodus, Tendergreen 08F-90, 990, NY, Sodus, Tendergreen 08G-90, 990, OR, Hillsbo, OSU 9 08H-90, 990, PA,NthamptonB urpee Stringless 08I-90, 990, TN, Toone, Contender 08J-90, 990, WI, Janesville, Hy-Style 08K-90, 990, WI, Delavan, Peak Aerial <0.08 Ground Ground Ground Aerial Ground Ground Ground Ground Aerial Ground

10 42 thiophanate-methyl Table 9. Thiophanate-methyl residues in soya bean hay from supervised trials in the USA (Castro, 998), Rept RD-II0209. location BR A,990, AR, Scott BR B, 990, BR C, 990, IA, Muscatine BR D,990, IA, Muscatine BR E, 990, IL, Carlyle BR G,990, IN, Hebron BR H,990, LA, Rosa BR I,990, MN, Theilman BR J,990, MO, Leonard BR K,990, MS, Hernando BR L,990, NE, Yk BR M,990, OH, New Holland Ground <0.2 <0.2 <0.3 Aerial Aerial < Ground < Ground < Ground < Ground Ground Ground < Ground < Ground <0.2 <0.2 <0.3 Ground < Table 0. Thiophanate-methyl residues in peanut hay from supervised trials in the USA (Bradway, 998), Rept RD-II Peanut plants were inverted 4 days after last application and dried f several days in the field. The one exception was trial J where hay and nuts were collected at the 4-day. location 0A-9, 99, AL, Grangerburg 0B-9, 99, AL, Grangerburg 0C-9, 99, 0D-9, 99, 0E-9, 99, 0F-9, 99, NC, Whitakers 0G-9, 99, NC, Whitakers 0H-9, 99, TX, Pattison 0I-9, 99, TX, Pattison 0J-9, 99, VA, Empia <0.5 <0.5 < <0.5 <0.5 < < <0.5 <0.5 <0.8 <0.5 <0.5 <0.8 < < <0.5 <0.5 <0.8 <0.5 <0.5 < <

11 thiophanate-methyl 43 Table. Thiophanate-methyl residues in sugar beet tops from supervised trials in the USA (Carr, 998), Rept RD-II Duplicate composite samples were collected from each treated plot (total residues as carbendazim are the mean of the two results). location , 997, MN, Mohead , 997, ND, Nthwood , 997, ND, Nthwood , 997, ND, Richland County , 997, MI, Conklin , 997, ND, Velva , 997, Levelland, TX , 997, Eaton, CO , 997, CA, Pterville , 997, Rupert, ID , 997, ID, Jerome Method kg ai/ha kg ai/hl No. WSB Seed ) + WSB Seed ) + WSB Seed ) + WSB Seed ) + WSB Seed ) + WSB Seed ) + WSB Seed ) + WSB Seed ) + WSB Seed ) + WSB Seed ) + WSB Seed ) + ) Seed treatment 0.25 kg ai/00 kg of seed ) ) ) ) ) ) ) ) ) ) ) ) Number of applications days TM MBC Total as MBC < mean mean mean mean mean mean mean mean mean mean mean 0.24

12 44 thiophanate-methyl NATIONAL MAXIMUM RESIDUE LIMITS The Meeting was aware of the national MRLs shown in Table 2. Table 2. National MRLs f thiophanate-methyl. Country Residue definition Commodity MRL, mg/kg Italy Sum of Cereals, Hops, Tea, Potato, Other fruits, vegetables, 0. carbendazim, oil seeds and pulses benomyl and Soybeans 0.2 thiophanate-methyl, Vegetable marrow 0.3 expressed as Brussels sprouts, Eggplant, Melon, Plum, Pumpkin, 0.5 carbendazim Tomatoes Apricot, Banana, Cucumber, Mushrooms, Peach Celery, Dry beans, Grapes, Pome fruits, Rhubarb 2 Head brassicas (except Brussels sprouts) 3 Citrus fruits, Lettuce 5 France Sum of Almond, Cabbage, Cherry, Garlic, Strawberry, 0. carbendazim, Onion, Peas, Potato benomyl and Eggplant, Melon, Plum, Tomato 0.5 thiophanate-methyl, Apricot, Peach expressed as Apple, Pear, Grape 2 carbendazim Germany Sum of Other plant commodities 0.05 carbendazim, Tea 0. benomyl and Soybean 0.2 thiophanate-methyl, Zucchini 0.3 expressed as Barley, Cucumber, Eggplant, Melon, Pumpkin 0.5 carbendazim Banana, Burdock, Cauliflower, Celery, Lettuce, Onion, Peas, Potato, Tomato, Turnip, Mushroom Strawberry,.5 Stone fruits 2 Grape 3 Citrus 5 Japan Sum of carbendazim Tea 20 and thiophanate- Fruits Vegetables 5 methyl, expressed Rice 2 as thiophanatemethyl Beans and Peas, Cereals except rice, Rot and Tubers, Sugar beet Netherlands Sum of Others 0. carbendazim, Soybeans 0.2 benomyl and Courgettes 0.3 thiophanate-methyl, Brussels sprouts, Eggplant, Melon, Plums, 0.5 expressed as Tomatoes, Winter squash carbendazim Apricots, Bananas, Cucumber, Mushrooms, Peaches, Nectarines Beans (dry), Celery, Table and wine grapes, Pome 2 fruit, Rhubarb Head cabbage 3 Citrus fruit, Lettuce 5

13 thiophanate-methyl 45 Country Residue definition Commodity MRL, mg/kg Spain Sum of Almonds, Cereals, Hazel nut, Sugar beet, Others 0. carbendazim, Zucchini 0.3 benomyl and Eggplant, Melon, Plums, Pumpkin, Tomato 0.5 thiophanate-methyl, Banana, Cucumber, Nectarine expressed as Apple, Beans (grain), Celery, Pear, Pome fruit, 2 Vines carbendazim Citrus, Lettuce 5 USA Thiophanate-methyl, Wheat grain 0.05 its oxygen analogue Sugarcane (seed piece treatment), Wheat hay and 0. [dimethyl-4,4 -o- straw phenylene-bis(allo- Almonds, Bananas (pulp), Peanuts, Pecans, 0.2 phanate)] Soybeans, Sugar beet roots and its Almonds hull, Cucumbers, Melons, Pumpkins, benzimidazole Squash containing Bananas, Beans dry and snap 2 metabolites Celery, Onions dry and green 3 expressed as Grapes, Strawberries 5 thiophanate-methyl Apricots, Cherries, Nectarines, Peaches, Peanuts 5 fage and hay, Plums, Prunes, Sugar beet tops Apple pomace dried 40 Beans fage and hay 50 REFERENCES Anonymous, Summary of Good Agricultural Practices f Pesticide Uses, thiophanate-methyl, February Federal Office f Consumer Protection and Food Safety, Division 2 Plant Protection Products Unit 223, D-3804 Braunschweig, Messeweg 2, Germany. Unpublished. Bradway, D. E. and Carr, B.L.998. Thiophanate Methyl and Its Metabolites: Magnitude of the Residue in Peanut. CAL Study Number , Nippon Soda Document No. RD-II02094, Centre Analytical Labaties, Inc. Unpublished. Burton, J Thiophanate Methyl and Its Metabolites: Magnitude of the Residue in Peanut. Analytical Rept BR-9-4. CAL Study Number , Nippon Soda Document No. RD-II02094, Centre Analytical Labaties, Inc. Unpublished. Carr, B. L Thiophanate-Methyl and Its Metabolites: Magnitude of the Residue in Summer Squash, Study Identification BR-9-3, Nippon Soda Document No. RD-II02092, Elf Atochem Nth America, Inc. Unpublished. Carr, B. L Thiophanate-Methyl and Its Metabolites: Magnitude of the Residue in Sugar Beet from the of Topsin M, Study Identification Elf Atochem Project Number KP-97-05, Nippon Soda Document No. RD-II02089, Elf Atochem Nth America, Inc. Unpublished. Castro, L Thiophanate-Methyl and Its Metabolites: Magnitude of the Residue in Soybean, Elf Atochem Study Identification BR-90-42, Nippon Soda Document No. RD-II0209, Elf Atochem Nth America, Inc. Unpublished. Chickering, C. D Stability of Thiophanatemethyl in Soybean Seed During Frozen Stage Pending Analysis, Cerexagri, Inc. Study ID KP-97-0, Nippon Soda Document No. RD-03033, Cerexagri, Inc. Unpublished. Hundley, S. G Residue Stability Study of MBC (Methyl-2-benzimidazole carbamate) in Snap Beans, Apples, Wheat Grain, Spinach, Sugar Beet Roots, and Tomatoes, Elf Atochem Study Number BR-87-6, Nippon Soda Document No. RD-03034, Elf Atochem Nth America, Inc. Unpublished.

14 46 thiophanate-methyl Leppert, B. C. and Castro, L Thiophanate- Methyl and Its Metabolites: Magnitude of the Residue in Snap Bean, Study Number BR-90-4, Nippon Soda Document No. RD-II02090, Elf Atochem Nth America, Inc. Unpublished. Leppert, B. C Thiophanate-Methyl and Its Metabolites: Magnitude of the Residue in Cherry, Study Number BR-9-27, Nippon Soda Document No. RD-II02093, Elf Atochem Nth America, Inc. Unpublished. Muller, E Summary of Good Agricultural Practices f Pesticide Uses, thiophanate-methyl, February Plant Protection Service, Wageningen, The Netherlands. Unpublished. Whitsel, M. K. 200a. Stability of Thiophanate-Methyl in Snap Beans During Frozen Stage Pending Analysis (Up To and Including 48 Months). Centre Study Number , Cerexagri Project Number KP- 96-, Nippon Soda Document No. RD-II02087, Centre Analytical Labaties Inc. Unpublished. Whitsel, M. K. 200b. Stability of Thiophanate- Methyl in Sugar Beets During Frozen Stage Pending Analysis (Up To and Including 48 Months). Centre Study Number , Cerexagri Project Number KP- 96-2, Nippon Soda Document No. RD-II02088, Centre Analytical Labaties, Inc. Unpublished. Williams, B. B.995. Analysis of Thiophanate-Methyl Residues in Snap Beans. Rept #4225, Nippon Soda Document No. RD-II02090, ABC Labaties. Unpublished. Williams, B. B Analysis of Thiophanate-Methyl Residues in Cherries. Elf Atochem Study Number BR- 9-27, Rept #4036, Nippon Soda Document No. RD-II02093, ABC Labaties. Unpublished. Williams, B. B Thiophanate-Methyl and Its Metabolites: Magnitude of the Residue in Soybean. Rept # 43782, Nippon Soda Document No. RD- II0209, ABC Labaties. Unpublished.