PESTICIDE RESIDUES IN FOOD - 1984 Sponsored jointly by FAO and WHO EVALUATIONS 1984 The monographs Data and recommendations of the joint meeting of the FAO Panel of Experts on Pesticide Residues in Food and the Environment and the WHO Expert Group on Pesticide Residues Rome, 24 September - 3 October 1984 Food and Agriculture Organization of the United Nations Rome 1985 DEMETON-S-METHYL AND RELATED COMPOUNDS (DEMETON-S-METHYL,OXYDEMETON-METHYL SULPHOXIDE), AND DEMETON-S-METHYL SULPHONE) Explanation One member of this group of compounds, oxydemeton-methyl (demeton-S-methyl sulphoxide), was reviewed at the 1965, 1967 and 1968 meetings1/. On the basis of the studies available at that time, primarily short-term studies, an acceptable daily intake for man was estimated at the 1965 meeting to be 0-0.0025 mg/kg/day. When further considered at the 1967 meeting new data, primarily a three-generation reproduction study, were reviewed and the ADI for man re-affirmed to be 0-0.0025 mg/kg/day. The 1968 meeting re-evaluated this compound and concluded that the available information revealed that the toxicology was not related to a single defined compound nor was there precise knowledge of the materials actually used in agricultural practice. Furthermore, no long-term data on any of the substances belonging to this group were available for evaluation. That meeting, therefore, recommended that the ADI as established at previous meetings should no longer be considered valid. The further work required to allow full assessment to be made included: specifications of the compound or compounds in actual agricultural use; studies to compare the metabolic fate in animals, plants and man; investigation of the cholinesterase inhibition in man and adequate long-term studies in two species. Some of these requirements were met and considered at the 1973 JMPR when an ADI of 0-0.005 mg/kg was estimated for the total of all three compounds. The 1981 JMPR identified this group of compounds (referred to, however, as "demeton and related compounds") as one for which the ADI was partially based on IBT data and the 1982 JMPR, in the absence of validated long-term toxicity studies, agreed to withdraw the ADI. As a consequence, the MRLs were withdrawn and replaced by GLs. Since then, data on current use patterns and new data on residues in various crops and commodities have become available and are reviewed together with new information on the stability of these compounds in soil, in this monograph addendum. RESIDUES IN FOOD AND THEIR EVALUATION USE PATTERN Demeton-S-methyl, oxydemeton-methyl and demeton-S-methyl sulphone are systemic compounds which have a fast action and long-lasting activity against sucking insect pests (aphids, thrips, whiteflies, hoppers, etc.) and spider mites. They also control pests with concealed habits. By giving good control of virus vectors, they very largely prevent fresh infections and virus disease spread. Each of the three compounds displays good crop compatibility. 1/ See Annex 2 for FAO and WHO documentation. Tables 1 to 4 summarize the currently recommended use patterns of demeton-S-methyl, oxydemeton-methyl and demeton-S-methyl sulphone. RESIDUES RESULTING FROM SUPERVISED TRIALS Tables 5, 6 and 7 summarize the new data on residues from extensive trials from 1974 to 1982 with all three compounds on a number of crops. In all analyses the residues were oxidised to the sulphone and calculated as demeton-S-methyl, the limit of determination being 0.01 mg/kg. FATE OF RESIDUES In animals An earlier study had shown no effects from feeding rations containing 5 ppm oxydemeton-methyl to poultry for 28 days. A further study (Thornton, 1975) was conducted to determine the effects, if any, of feeding higher levels of oxydemeton-methyl to chickens. Poultry rations containing 15 and 30 ppm oxydemeton-methyl, were fed continuously for 28 days. At the end of that period, the birds were sacrificed and tissues and eggs were analyzed for residues. Twelve laying hens (breed, Babcock 300), approximately 25 weeks old, were caged individually and fed and watered ad lib. for a two-week period which was sufficient to establish good egg production and feed consumption. Residue analysis of muscle, giblet, skin and fat tissues showed no detectable residues of oxydemeton-methyl in the chickens fed 15 ppm fortified feed. At the 30 ppm level, no detectable residues were found in any tissue except giblets which all contained 0.01 mg/kg. However, this value is at the extreme limit of sensitivity for tissue analyses and cannot be considered significant. Twenty-eight day egg residues from chickens fed 15 ppm showed measurable residues of 0.002 mg/kg which is near the limit of determination of the method for eggs. At the 30 ppm feeding level, residues were measured up to 0.005 mg/kg. In soil A 5 mg/l aqueous solution of oxydemeton-methyl (methoxy-14C) irradiated with light from the visible and ultraviolet portion of the spectrum did not appear to be rapidly degraded. The half-life of the parent compound under these conditions was 16 days. By comparison, the half-life of oxydemeton-methyl in a solution containing 2% acetone as a triplet sensitizer was 4 days. Degradation products in the aqueous solution included demeton-S-methyl sulphone, dimethyl phosphate and dimethyl phosphorothioate. Oxydemeton-methyl irradiated on the surface of silt loam soil did not appear to be significantly altered by light in comparison to degradation by other factors (Nichols and Thornton, 1978). Table 1. Use pattern of demeton-S-methyl Europe Asia Africa Australia South and and New Central Zealand America Sugar and fodder beet 125-200 g/ha X X Potatoes 175-400 g/ha X X X Pome fruit 0.025 % X X X (apples, pears) Cereals 75-125 g/ha X X X Ornamentals, X X tree nurseries Table 2. Use pattern of oxydemeton-methyl Europe Asia Africa Australia South and and New Central Zealand America Sugar and fodder beet 125-200 g/ha X X Potatoes 175-400 g/ha X X X Pome fruit 0.025 % X X X X (apples, pears) Stone and small fruit 0.025 % X X X Apricots Strawberries Currants Cherries Peaches Plums Grapes 0.025 % X X X Cereals 75-125 g/ha X X Maize, Sorghum 175-200 g/ha X X Citrus fruit 0.025 % X X X X Alfalfa 250 g/ha X Table 2. (continued) Europe Asia Africa Australia South and and New Central Zealand America Vegetables 125-300 g/ha X X X X Eggplants Beans Broccoli Peas Cucumbers Brassicas (Kale, Brussels sprouts, Cauliflower) Kohlrabi Pumpkins, Squash Melons Carrots Head Lettuce Tomatoes Onions Ornamentals, X X tree nurseries X X Table 3. Use pattern of demeton-S-methyl sulphone (in "Gusathion MS"*) Europe Asia Africa Australia South and and New Central Zealand America Pome fruit 0.015 % X X Apples, pears Stone and small fruit 0.015 % X Strawberries, currants cherries, plums Grapes 0.015 % X * "Gusathion MS" also contains azinphos-methyl. Table 4. Use pattern of oxydemeton-methyl in the USA Crops Dose, a.i. Cotton 437 - 585 g/ha Corn 437 - 585 g/ha Sorghum 292 - 585 g/ha Sugar beets 437 - 877 g/ha Alfalfa 437 - 585 g/ha Blackberries, Raspberries 0,032 - 0,047 % Grapes, Lemons, Oranges 0,032 - 0,047 % Pears 0,032 % Plums, Prunes 0,032 % Strawberries 437 - 877 g/ha Beans 585 g/ha Broccoli, Brussels sprouts, Cauliflower 437 - 585 g/ha Cabbage 437 - 877 g/ha Cucumbers 437 - 585 g/ha Eggplant 585 g/ha Head lettuce 437 - 585 g/ha Spanish onions (bulb) 877 g/ha Peas 437 g/ha Peppers 585 g/ha Potatoes 437 - 585 g/ha Pumpkin, Squash (Winter and Summer) 437 - 585 g/ha Turnips 437 - 585 g/ha Muskmelon (cantaloupe), other melons 437 - 587 g/ha Watermelons 437 - 585 g/ha Walnuts 0,047 % Table 5. Residues of demeton-S-methyl in sugar beet, potatoes and apples Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Sugar beets 200 g/ha 3-4 FRG BAYER Roots 0 0.06 0.06 (1) 4903 - 13 <0.01 <0.01 (1) 4904/75 21 n.d. n.d. (1) 4900 - 28/30 n.d. -<0.01 <0.01 (4) 4902/77 35 n.d. n.d. (3) 42/43 n.d. n.d. (3) 59-85 n.d. n. d. (6) Leaves 0 2.57 2.57 (1) 13 0.24 0.24 (1) 21 <0.01 <0.01 (1) 28/30 n.d. - 0.02 <0.01 (4) 35 n.d. n.d. (3) 42/43 n.d. n.d. (3) 59-85 n.d. n.d. (6) Potatoes 200 - 3 FRG 0 0.06 - 0.11 0.08 (3) BAYER 300 g/ha 14 <0.01 - 0.01 0.01 (3) 4900 - 21/22 0.01 - 0.05 0.02 (3) 4902/74 28/29 <0.01 <0.01 (3) Apples 0.025 4 FRG 0 0.81 - 0.88 0.85 (3) 4900 - 7 0.48 - 0.64 0.54 (3) 4902/75 14 0.47 - 0.59 0.52 (3) 21 0.42 - 0.54 0.47 (3) 28 0.25 - 0.41 0.33 (3) Values in parentheses indicate number of individual results. Table 6. Residues from the use of oxydemeton-methyl in trials on various crops Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Sugar beets 200 g/ha 4 FRG Roots 0 0.02 - 0.05 0.03 (3) BAYER 28 0.02 - 0.05 0.03 (3) 4842 - 35 0.02 - 0.05 0.03 (3) 4844/79 42 0.02 - 0.05 0.03 (3) 49 0.02 - 0.05 0.03 (3) 77-88 0.02 - 0.05 0.04 (3) Leaves 0 1.11 - 2.02 1.58 (3) 28 0.02 - 0.03 0.03 (3) 35 0.02 - 0.03 0.03 (3) 42 0.02 - 0.34 0.13 (3) 49 0.02 - 0.36 0.14 (3) 77-88 0.02 - 0.03 0.03 (3) Potatoes 200 - 3 FRG 0 <0.02 - 0.04* 0.03 (3) BAYER 300 g/ha 14 0.04 - 0.10* 0.07 (3) 4800 - 21/22 0.02 - 0.08* 0.04 (3) 4802/74 28 0.04* 0.04 (1) Apples 0,025 % 4 FRG 0 <0.04 - 1.9 0.74 (6) BAYER 10/14 <0.04 - 1.5 0.54 (6) 4823 - 21 <0.04 - 0.96 0.33 (6) 4824/75 28 <0.04 - 0.56 0.22 (6) 4806 - 35 <0.04 - 0.46 0.24 (6) 4807/82 4819 - 4820/82 Table 6. (continued) Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Pears 0.025 % 4 FRG 0 0.04 - 1.7 0.71 (4) BAYER 10 <0.01 - 0.67 0.26 (4) 4809 - 21 n.d. - 0.49 0.16 (4) 4810/82 28 n.d. - 0.33 0.12 (4) 4821 - 35 n.d. - 0.30 0.10 (4) 4822/82 Strawberries 0.025 % 2 FRG 0 0.41 - 0.58 0.50 (2) BAYER 7 0.23 0.23 (2) 4808 - 14 0.09 - 0.11 0.10 (2) 4809/76 21 0.03 - 0.06 0.05 (2) 28 0.02 0.02 (2) Currants, black 0.025 % 2 FRG 0 1.9 - 9.2 5.71 (6) BAYER 7 0.89 - 4.02 3.02 (6) 4800 - 12/14 0.50 - 2.4 1.65 (6) 4802/76 19/21 0.41 - 1.59 1.13 (6) 4834 - 26/28 0.22 - 1.33 0.79 (6) 4836/79 33/35 0.30 - 0.73 0.49 (4) 40 0.24 0.24 (1) Currants, red 0.025 % 2 FRG 0 2.87 - 7.91 5.22 (6) BAYER 7 0.55 - 5.16 2.65 (6) 4803 - 14 0.42 - 4.40 1.87 (6) 4805/76 21 0.37 - 2.61 1.50 (6) 4837 - 28 0.41 - 1.17 0.91 (6) 4839/79 35 0.28 - 1.28 0.69 (3) Table 6. (continued) Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Cherries 0.025 % 4 FRG 0 1.08 - 2.16 1.76 (3) BAYER 7 1.01 - 1.57 1.26 (3) 4825- 14 <0.04- 1.39 0.52 (3) 4827/79 21 0.12 - 1.32 0.58 (3) 28 <0.04 - 0.62 0.41 (3) Peaches 0.025 % 4 FRG 0 <0.04 - 6.0 2.22 (6) BAYER 7 <0.04 - 1.3 0.64 (6) 465- 14 <0.04 - 1.3 0.53 (6) 467/73 21 <0.04 - 0.56 0.23 (6) 4832/79 28 <0.04 - 0.4 0.18 (6) 4805 - 4806/80 Plums 0.025 % 2-4 FRG 0 0.12 - 0.76 0.37 (6) BAYER 7 0.1 - 0.60 0.25 (6) 462 - 14 <0.04 - 0.41 0.21 (6) 464/73 21 0.06 - 0.61 0.27 (6) 4828 - 28 0.08 - 0.24 0.14 (6) 4830/79 Grapes 0.025 % 3 FRG 0 0.55 - 1.9 1.11 (5) BAYER 21 0.5 - 1.4 0.88 (5) 4837- 28 0.05 - 0.87 0.55 (5) 4839/75 55 0.1 - 0.55 0.43 (5) 4840 - 42 0.06 - 0.75 0.41 (5) 4841/79 49 0.07 - 0.7 0.41 (5) 62 0.05 0.05 (1) Must 0.07 - 0.65 0.36 (3) Table 6. (continued) Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Wine 0.08 - 0.4 0.26 (3) 0.045 - 2 USA 49 0.42 - 1.21 0.93 (3) MOBAY 0.075 % 56/58 0.10 - 0.72 0.40 (4) 45057, 61/63 <0.05- 2.43 0.92 (4) 43063, 72 0.19 0.19 (1) 69786, 91-151 <0.05 <0.05 (6) 69800, 69801, Juice 122 <0.05 <0.05 (1) 69803 Wet pomace 122 <0.05 <0.05 (1) Dry pomace 122 <0.05 <0.05 (1) Barley 125 g/ha 2 FRG BAYER Green forage 0 2.0 - 2.9 2.5 (3) 4803 7 0.33 - 3.2 1.88 (3) 4805/82 14 0.11 0.11 (1) Ears 0 1.6 - 3.8 2.47 (3) 7 0.38 - 3.5 1.63 (3) 14 0.12 0.12 (1) Straw 14 0.65 - 1.1 0.88 (2) 21 <0.01 - 0.97 0.36 (3) 28 <0.01 - <0.02 <0.02 (3) Grains 14 0.04 - 0.25 0.15 (2) 21 <0.01 - 0.1 0.05 (5) 28 <0.01 - 0.08 0.04 (3) Table 6. (continued) Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Oats 125 g/ha 2 FRG Green forage 0 0.48 - 2.5 1.57 (3) BAYER 7 0.01 - 1.7 1.00 (3) 4800 - 14 0.01 - 0.77 0.31 (3) 4802/82 Ears 0 0.25 - 3.40 1.78 (3) 7 0.18 - 1.7 0.96 (3) 14 0.18 - 1.1 0.67 (3) Straw 21 <0.02 - 0.12 0.07 (3) 28 <0.02 - 0.17 0.06 (3) Grains 21 <0.02 - 0.08 0.03 (3) 28 <0.02 - 0.03 0.02 (3) Wheat 200 g/ha 2 FRG BAYER Green forage 0 1.63 1.63 (1) 4800- 7 0.28 0.28 (1) 4802/79 14 0.33 0.33 (1) Ears 0 0.27 - 1.80 1.07 (3) 7 <0.05 - 0.24 0.16 (3) 14 <0.02 - 0.09 0.04 (5,) 21 <0.02 <0.02 (1) Straw 0 <0.05 - 1.60 0.81 (2) 7 <0.05 <0.05 (2) 14 <0.05 <0.05 (2) 21 <0.05 - 0.04 <0.05 (2) 28 <0.05 - 0.02 <0,05 (3) 35 n.d. n.d. (1) 42 n.d. n.d. (1) Table 6. (continued) Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Grains 21 <0.05 - 0.07 <0.05 (2) 28 <0.02 - 0.22 0.09 (3) 35 n.d. n.d. (1) 42 n.d. n.d. (1) Corn 560 g/ha 3 USA MOBAY Green forage 0 2.18 - 16.7 10.23 (7) 67456, 3 0.30 - 10.4 3.87 (7) 67457, 7 0.98 - 4.87 1.90 (6) 67459, 14 0.15 - 3.36 1.53 (4) 67491 - 21 0.10 - 2.73 0.85 (4) 67494 Milk stage 0 <0.01 - 0.06 0.03 (7) kernel 3 <0.01 - 0.04 0.02 (3) 7 <0.01 <0.01 (3) 14 <0.01 <0.01 (3) 21 <0.01 <0.01 (3) Milk stage 0 <0.01 - 0.16 0.04 (7) cob 3 <0.01 - 0.07 0.03 (3) 7 <0.01 - 0.01 <0.01 (5) 14 <0.01 <0.01 (3) 21 <0.01 <0.01 (5) Milk stage 0 0.19 - 1.69 0.84 (7) husk 3 0.05 - 0.98 0.64 (3) 7 0.27 - 0.56 0.41 (3) 14 <0.01 - 0.56 0.25 (3) 21 <0.01 - 0.09 0.04 (5) Table 6. (continued) Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Dry Forage 52/64 <0.01 - 0.13 0.07 (3) Dry kernel 52/64 <0.01 <0.01 (3) Dry cob 52/64 <0.01 <0.01 (3) Dry husk 52/64 <0.01 - 0.04 0.02 (3) Sorghum 560 g/ha 3 USA MOBAY Forage 7 1.88 - 2.63 2.26 (2) 41027, 14-16 0.15 - 2.59 0.70 (11) 41028, 21 0.13 - 0.66 0.41 (3) 41031, 28-31 0.09 - 0.22 0.16 (8) 41055, 55 0.09 - 0.18 0.14 (3) 43449, 42/45 0.04 - 0.16 0.12 (7) 46356, 46357, Grain 7 0.24 - 0.31 0.28 (2) 46545, 14/15 0.05 - 3.00 0.88 (7) 46547, 20/21 0.03 - 1.10 0.58 (4) 46549, 28 <0.01 - 1.11 0.41 (4) 46550, 35 0.03 - 0.86 0.38 (5) 46553, 42/45 0.02 - 0.62 0.23 (8) Alfalfa 560 g/ha 1 USA 0 6.72 -21.2 12.47 (5) MOBAY 7 1.17 -18.0 5.68 (5) 51193, 14 0.20 - 5.09 1.68 (5) 51199, 21 <0.05 - 1.10 0.32 (5) 51200, 28 0.58 0.58 (1) 51221, 51383 Table 6. (continued) Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Beans 560 g/ha 2 USA MOBAY Dry beans 41-48 <0.01 <0.01 (10) 54122, 55-62 <0.01 <0.01 (10) 66523, 69-76 <0.01 <0.01 (10) 66525, 66681, Dry vines 41-48 <0.01- 0.12 0.02 (10) 67180 60-62 <0.01 - 0.05 0.01 (10) 67185 75/76 <0.01 - 0.05 <0.01 (10) Bush-beans 225 g/ha 3 FRG BAYER Beans 0 <0.02 - 0.05 0.03 (2) 4819 - 4 <0.02 - 0.05 0.03 (2) 4820/79 7 <0.04 - 0.05 <0.04 (2) 14 <0.04 - 0.05 <0.04 (2) 21 <0.04 - 0.05 <0.04 (2) Pods 0 0.04 - 0.06 0.05 (2) 4 n.d. - <0.04 <0.04 (2) 7 n.d. - <0.04 <0.04 (2) 14 n.d. - <0.04 <0.04 (2) 21 n.d. - <0.04 <0.04 (2) Straw 0 1.83 - 2.09 1.96 (2) 4 0.1 - 0.76 0.43 (2) 7 0.04 - 0.24 0.14 (2) 14 0.04 0.04 (2) 21 <0.03 - 0.04 <0.05 (2) Table 6. (continued) Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Pole-beans 300 g/ha 3 FRG 0 <0.04 - 0.56 0.29 (2) BAYER 4 <0.04 - 0.41 0.22 (2) 4821 - 7 <0.04 - 0.25 0.14 (2) 4822/79 14 <0.04 - 0.07 0.05 (2) 21 <0.04 <0.04 (2) Peas 150 - 2-3 FRG BAYER Peas and pods 225 g/ha 0 0.08 - 0.32 0.19 (3) 4856 - 4858/75 Peas 0 <0.05 - <0.06 <0.05 (2) 4811 - 4 <0.05 - <0.06 <0.05 (2) 4812/79 7 <0.05 - <0.06 <0.05 (2) 14 <0.02 - 0.07 <0.05 (5) 21 <0.02 - 0.05 <0.05 (5) 28 <0.02 - 0.04 <0.05 (2) 35 <0.02 - <0.04 <0.05 (2) Pods 0 <0.05 - <0.06 <0.05 (2) 4 <0.05 - <0.06 <0.05 (2) 7 <0.05 - <0.06 <0.05 (2) 14 0.02 - <0.06 <0.05 (5) 21 0.01 - <0.06 <0.05 (5) 28 0.01 - 0.04 <0.05 (2) 35 <0.02 - <0.04 <0.05 (2) Straw 0 0.40 - 2.32 1.66 (3) 14 <0.05 - <0.06 <0.05 (2) 21 <0.05 <0.05 (1) 35 0.01 - <0.04 0.02 (2) Table 6. (continued) Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Cucumbers 150 g/ha 3 FRG 0 <0.02 - <0.05 <0.02 (3) BAYER 1 <0.02 - <0.05 <0.02 (3) 4813 - 4 <0.04 - 0.06 <0.04 (3) 4815/79 7 <0.04 - <0.05 <0.04 (3) 14 <0.04 - <0.05 <0.04 (3) Kale 150 g/ha 2 FRG 0 1.69 - 3.48 2.59 (2) BAYER 7 <0.06 - 0.28 0.16 (2) 4809 - 14 <0.05 - 0.10 0.06 (2) 4810/79 21 <0.05 - 0.09 0.06 (2) 28 n.d. - <0.05 <0.05 (2) Brussels 250 g/ha 1 NL 29 n.d. n.d. (2) BAYER sprouts 4808 - 4809/78 560 g/ha 3 USA 0 0.24 - 2.75 1.42 (5) MOBAY 3/4 0.10 - 1.62 0.77 (5) 68695, 7 0.06 - 0.96 0.46 (4) &9177, 10 0.02 - 0.47 0.26 (5) 82487 - 14/17 0.02 - 0.71 0.31 (5) 82489 Cauliflower 150 g/ha 2 FRG BAYER Heads 0 <0.03 - <0.05 <0.05 (2) 4810 - 7 <0.03 - <0.05 <0.05 (2) 4812/76 14 <0.03 - <0.05 <0.06 (2) 4805 - 21 <0.03 - <0.05 <0.05 (2) 4806/79 28 <0.03 - <0.05 <0.05 (2) Table 6. (continued) Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Stalks 0 <0.02 - <0.05 <0.05 (2) 7 <0.02 - <0.05 <0.05 (2) 14 <0.02 - <0.05 <0.05 (2) 21 <0.02 - <0.05 <0.05 (2) 28 <0.02 - <0.05 <0.05 (2) Cauliflower, 0 0.08 - 0.21 0.17 (3) total 7 <0.01 - 0.01 <0.01 (3) 14 <0.01 <0.01 (3) 21 n.d. n.d. (3) 28 n.d. n.d. (3) White cabbage 150 g/ha 2 FRG 0 0.70 0.70 (1) BAYER 7 <0.04 <0.04 (1) 4805/79 14 <0.04 <0.04 (1) 21 <0.04 <0.04 (1) 28 <0.04 <0.04 (1) Savoy Cabbage 150 g/ha 2-3 FRG 0 0.35 - 2.55 1.16 (4) BAYER 7 0.03 - 0.15 0.08 (3) 4827/75 14 n.d. - 0.04 <0.04 (4) 4829/75 21/22 n.d. - 0.05 <0.05 (4) 4850/75 28/29 n.d. n.d. (4) 4817/76 36 n.d. n.d. (1) Kohlrabi 150 g/ha 2 FRG BAYER Tuber 0 n.d. - <0.06 <0.06 (2) 4804/79 7 n.d. - <0.06 <0.06 (2) 4800/80 14 n.d. - <0.06 <0.06 (2) 21 n.d. - <0.06 <0.06 (2) 28 n.d. - <0.06 <0.06 (2) Table 6. (continued) Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. Leaves 0 0.48 - 3.59 2.04 (2) 7 <0.06 - 0.62 0.33 (2) 14 <0.06 - 0.22 0.13 (2) 21 n.d. - <0.06 <0.06 (2) 28 n.d. - <0.06 <0.06 (2) Leek 150 g/ha 2 FRG 0 0.29 - 0.61 0.45 (2) BAYER 7 <0.04 <0.04 (2) 4807 - 14 <0.04 <0.04 (2) 4808/79 21 <0.04 <0.04 (2) 28 <0.04 <0.04 (2) Head Lettuce 150 g/ha 1 FRG 0 2.0 - 9.1 5.74 (6) BAYER 8 0.25 - 0.79 0.59 (6) 4800 - 14 0.05 - 0.48 0.21 (6) 4802/75 21 0.01 - 0.09 0.03 (6) 4824 - 28 0.01 - 0.02 0.01 (6) 4826/75 560 g/ha 1-3 USA 0 8.15 - 9.58 8.87 (2) MOBAY 3 5.79 - 15.8 9.34 (5) 39674- 6/7 0.16 - 12.5 4.04 (15) 39676, 10-15 0.06 - 5.74 1.37 (25) 41156 - 20-25 <0.01 - 2.85 0.65 (26) 41165, 24-28 <0.04 - 1.35 0.62 (11) 67466, 35 0.10 0.10 (1) 67478 - Table 6. (continued) Crops Dose a.i. No. of Country Interval, Residue mg/kg Report applications days range average No. 42 0.09 0.09 (1) 67480, 67483, 67653 - 67655, 67929 - 67931, 67957, 69462 - 69465 Tomatoes 150 - 3-4 FRG 0 <0.04 - 0.12 0.09 (6) BAYER 225 g/ha 1 <0.04 - 0.29 0.13 (6) 4803 - 4 <0.04 - 0.05 <0.04 (5) 4805/75 7 <0.02 - 0.19 0.08 (6) 4816 - 14 <0.04 - 0.11 0.07 (6) 4818/79 Bulb onions 840 g/ha 3-4 USA 30/31 <0.01 - 0.02 <0.01 (11) MOBAY 31518 - 31523, 31577 - 31579, 31632, 31691 Peppers 560 g/ha 2 USA 0 n.d - 4.9 0.7 (9) MOBAY 2-4 0.1 - 1.6 0.4 (9) 18311 - 6/7 n.d. - 2.(] 1.0 (2) 18317 14 0.2 - 0.7 0.5 (2) 18329, 18330 Table 6. (continued) Residues calculated as demeton-S-methyl * Residues calculated as demeton-S-methyl sulphoxide Values in parentheses indicate number of individual results. Table 7. Residues from the use of Demeton-S-methyl sulphone in trials on various crops Crops Dose a.i. No. of Country Residue mg/kg Report applications Interval, range average No. days Apples 0.015 % 4-6 FRG 0 0.21 - 0.89 0.43 (7) BAYER 10 <0.01 - 0.33 0.16 (3) 4201/78 14 0.10 - 0.36 0.21 (4) 4200 - 21 <0.01 - 0.33 0.15 (7) 4202/79 28 n.d. - 0.47 0.12 (7) 4200 - 35 n.d. - 0.37 0.09 (Z) 4201/82 4210/82 Pears 0.015 % 4-5 FRG 0 0.01 - 0.49 0.29 (3) BAYER 10 n.d. - 0.25 0.13 (3) 4203 - 21 n.d. - 0.09 0.05 (3) 4204/82 28 n.d. - 0.07 0.04 (3) 4211/82 35 n.d. - 0.06 0.03 (3) Strawberries 0.015 % 4-5 FRG 25 0.05 - 0.06 0.06 (2) BAYER 28 0.02 - 0.04 0.03 (3) 459 - 34 0.01 - 0.02 0.02 (3) 461/73 41 n.d. n.d. (3) Currants, black 0.015 % 3 FRG 0 1.24 - 2.53 1.82 (3) BAYER 7 0.84 - 1.33 1.10 (3) 4203 - 14 0.46 - 0.55 0.49 (3) 4205/76 21 0.29 - 0.59 0.43 (3) 28 0.15 - 0.22 0.18 (3) 35 0.05 - 0.10 0.08 (3) Table 7. (continued) Crops Dose a.i. No. of Country Residue mg/kg Report applications Interval, range average No. days Currants, red 0.015 % 3 FRG 0 0.42 - 1.02 0.70 (3) BAYER 21 0.07 - 0.54 0.23 (3) 4203- 28 0.04 - 0.32 0.13 (3) 4205/75 35 0.03 - 0.12 0.06 (3) 42 0.04 - 0.14 0.07 (3) Cherries 0.015 % 3 FRG 0 1.58 - 2.33 2.00 (3) BAYER 14 0.69 - 1.06 0.78 (3) 4204 - 21 0.37 - 0.55 0.45 (3) 4206/78 28 0.19 - 0.22 0.20 (3) 35 0.14 - 0.27 0.19 (3) Plums 0.015 % 5 FRG 0 0.04 - 1.1 0.54 (5) BAYER 14 0.05 - 1.6 0.44 (5) 4202 - 21 0.07 - 0.57 0.25 (5) 4203/78 28 0.05 - 0.56 0.25 (5) 4203 - 35 0.04 - 0.54 0.22 (5) 4205/79 Grapes 0.015 % 3 FRG 0 0.13 - 2.14 0.92 (7) BAYER 35 0.04 - 0.85 0.34 (7) 4207/77 42 0.03 - 0.34 0.17 (7) 4207 - 49 0.03 - 0.26 0.14 (7) 4210/78 56 0.02 - 0.34 0.13 (7) 4206 - 63 0.02 - 0.17 0.10 (2) 4207/79 Must 49-63 0.01 - 0.48 0.09 (8) Wine 49-65 0.01 - 0.5 0.11 (8) Residues calculated as demeton-S-methyl Values in parentheses indicate number of individual results. Demeton-S-methyl sulphone was not found to be degradable by direct irradiation in the environment, (Wilmes 1982). In a study of the soil thin-layer mobility of 24 pesticides on six different soil types ranging from a non-adsorptive sand to a fine-textured clay, oxydemeton-methyl showed a relatively high mobility related to its relatively high solubility in water (Thornton et al, 1976). Oxydemeton-methyl (methoxy-14C) was incubated at 23°C for 60 days with a silt loam and a loamy soil. Seventy-five and 79% of the radioactivity was recovered as 14CO2 during that period, respectively. Only 1% of the activity was organosoluble at that time. Small amounts of residue were associated with water-soluble and mineral residues, and with humic and fulvic acids. Most of the fulvic acid residues was dializable (Houseworth and Tweedy, 1974). Oxydemeton-methyl was extensively degraded on silt under aerobic conditions, as shown by the generation of large amounts of 14CO2 from both the ethylene- and the methoxy-label (59% and 79% after 57 and 49 days respectively). Nearly all of the remaining 14C from each label was unextractable. The degradation of the parent compound under anaerobic conditions was also fast (half-life of less than one day), but was not complete since after 57 days 24% of the 14C was still extractable while only 8% appeared as 14CO2. Four water-soluble soil metabolites were identified together with five organosoluble metabolites. Metabolic pathways are shown in Figure 1 (Phul and Hurley, 1978). Oxydemeton-methyl is degraded by Pseudomonas putida 1453 by cleavage of the thioester bond to form three major compounds: 2-(ethylsulphinyl) ethanethiol, 2-(ethylsulphonyl) ethanethiol and bis/-2-(ethylsulphinyl) ethyl/disulphide. Nocardia sp. DSM 43252 converts the insecticide into another three metabolites: bis/-2-(ethylsulphonyl)ethyl-disulphide,bis-2-(ethylsulphinyl ethyl-sulphide, and bis-2-(ethylsulphonyl)ethyl-sulphide, via oxidation, elimination and hydrolysis. 0,0-Dimethyl phosphorothioate had been detected in the aqueous layer of the medium (Ziegler et al, 1980). Twenty-eight days after the application of -ethylene-1-14C-demeton-S-methyl sulphone to soil (standard soil 1, type 2.2 as specified in BBA (Federal Biological Agency) Bulletin No. 36, 2nd edition, 30% of the 14C activity was seen to have been eliminated as 14CO2. The following transformation products of demeton-S-methyl sulphone representing intermediates in mineralization, were isolated and identified by nuclear magnetic resonance spectroscopy and mass spectrometry. 2-Ethylsulphonylethane sulphonic acid (VI) was identified as the main transformation product of demeton-S-methyl sulphone in soil. The concentration of this highly polar compound increased continuously with time, reaching a maximum of 10.8% of the applied radioactivity after 73 days. The markedly less polar 2-ethylsulphonylethanethiol (IV), soluble in water and methanol, accounted for up to 3.7%. The highly polar compound (II) peaked at a concentration of 4.9% after 31 days. After 126 days, it was still detectable at a concentration of 1.9%/(III) was detectable only in very small amounts (<1%). The relatively non-polar oxidation product of IV, the disulphide (V), reached a maximal concentration of 2.2% after 73 days. After 126 days, it was detectable only in very small amounts (0.66%). A non-polar degradation product VII (1.1% of the applied 14C) could not be identified. In comparison with the 14CO2 balance study, the experiments to identify the structures of the degradation products were conducted with substantially higher parent compound concentrations. It is known that a highly increased parent compound concentration may lead to delayed mineralization. On the other hand, this frequently results in an accumulation of intermediates which under "normal" reaction conditions can be detected only with difficulty or perhaps not at all. Figure 2 shows the probable pathways of demeton-S-methyl sulphone degradation in soil (Wagner and Oehlmann, 1980). To study the effects of plant growth and time on residues of 14C oxydemeton-methyl in soil, corn and cotton were grown in [14C] oxydemeton-methyl treated soil and harvested. After the soil had lain fallow, alfalfa and corn were grown in the treated soil, a portion of which had been extracted with methanol/water, and subsequently harvested. [14C] oxydemeton-methyl treated soils contained 16% of the radioactivity as residue when the initial corn and cotton plants were harvested. These plants absorbed 1.2% of the applied material. Soils still contained 13% of the radioactivity(all was bound) one year after treatment. Rotational crops of alfalfa and corn, grown in extracted 14C. No significant difference in residue uptake was detected between plants grown in extracted and non-extracted soil (Shaw II, 1975). RESIDUES IN FOOD IN COMMERCE OR AT CONSUMPTION United Kingdom, 1982 Samples of lettuce taken at the point of retail sale (July 1981 - April 1982) were analysed, using a multi-residues procedure. The limit of determination of demeton-S-methyl (as the sulphone) was 0.01 mg/kg and the recovery 80%. Results are shown in Table 8. Table 8. Residues of demeton-S-methyl in lettuce at point of retail sale. Total number Residues range Number in analysed mg/kg range Home-grown(UK) 65 < 0.1 56 0.1 - 0.5 5 0.5 - 1.0 3 2.6 1 Imported 101 < 0.1 101 166 166 A further 47 samples of imported lettuce (22 from The Netherlands, 8 from the U.S.A., 6 from Spain, 5 from Israel, 4 from France, 1 each from Rumania and Cyprus) were examined for a range of organophosphorus pesticide residues in late 1981. The modified Watts et al. method with oxidation step was used. Recoveries were 80-95% and the limit of determination less than one tenth of the MRL. No residues of the demeton-S-methyl group were found in these samples. 24 samples of top fruit, obtained direct from growers in the UK in 1982, were examined for a range of pesticides using a multi-residues procedure. Recovery of added demeton-S-methyl, determined as the sulphone, was 90-100%. Three samples had been sprayed with a demeton-S-methyl formulation and the residues data obtained were: Date of Interval between Residues, Samples harvest last application mg/kg and harvest (days) Apples: Discovery 20/8 54 < 0.05 Millers seedlings 20/8 54 < 0.05 Plums: 2/8 84 < 0.05 Residues data on soft fruit both from retail outlets and direct from growers were obtained in May-August 1982. A range of pesticides was analysed for, using a multi-residues procedure. The limit of determination was 0.05 mg/kg and recoveries were 66% and 75%. Results are shown in Table 9. Samples were also obtained direct from growers (17 strawberries, 6 gooseberries, 14 currants, 16 berries) and only one sample (of gooseberries) showed detectable residue of demeton-S-methyl (0.10; 0.25mg/kg) after 32 days between last application and harvest. METHODS OF RESIDUE ANALYSIS Hill et al. (1984) have reported a study on the experimental conditions for the routine quantitative determination of the residues of a number of organophosphorus pesticides, including demeton-S-methyl, following conversion to the sulphones. NATIONAL MAXIMUM RESIDUE LIMITS National MRLs, as listed in Table 10, were reported to the meeting (effective March 1983). APPRAISAL The meeting considered data from residue trials on a number of crops. In general the results of the trials support the maximum residue levels previously estimated in 1973 and enabled the meeting to estimate maximum levels for several new commodities, namely cherries (1 mg/kg), kale (0.2), bulb vegetables (0.1, tomatoes (0.2) and peppers (1). The meeting proposed a group GL of 0.2 mg/kg for brassica leafy vegetables to replace separate GLs of 0.2 mg/kg for broccoli, Brussels sprouts, cabbage, cauliflower and kale. The commodity description of cereals ("raw cereals") was redefined as "cereal grains." Table 9. Demeton-S-methyl residues in retail samples of soft fruit Fruit Number of samples Residues mg/kg examined Strawberries (UK-produced) 23 one 0.16; one 0.79; others not detectable (ND) Strawberries (imported) 18 ND Gooseberries (UK) 8 ND Black/red currants (UK) 13 ND Berries (raspberries, loganberries, blackberries) (UK) 15 ND Table 10. National Maximum Residue Limits Oxydemeton-methyl Country Crop/Commodity Safety MRL intervals (mg/kg) (days) Australia 1) cereals 0.5 herbs 0.5 hops 0.5 macadamia nuts 0.05 2) oil seed 0.5 pome fruit 0.5 stone fruit 0.5 strawberries 0.5 tomatoes 0.5 vegetables 0.5 water 0.03 Austria cereals 35 0.4 3) fruit 35 0.4 3) potatoes 35 0.2 3) sugar beets 35 0.4 3) vegetables (excl. 35 0.4 3) carrots) other crops 0.05 3) Belgium carrots 28 0 3) fruit (excl. citrus) 28 0.4 3) potatoes 28 0.1 3) sugar beets 28 vegetables (excl. 28 0.4 3) carrots) Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) Brazil 3) apples 1.0 barley 0.2 cotton 0.2 cucumbers 0.2 eggplants 0.2 maize 0.2 melons 0.2 oats 0.2 peaches 1.0 pears 0.5 plums 1.0 potatoes 0.2 pumpkins 0.2 quinces 0.5 rice 0.2 rosemallow 0.05 2) rye 0.2 sorghum 0.2 tomatoes 0.5 wheat 0.2 eggs (shell-free) 0.05 2) meat 0.05 2) milk 0.05 2) Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) Canada barley 0.1 2) beans 0.1 2) brassicas 0.1 2) caneberries 0.1 2) cucumbers 0.1 2) maize 0.1 2) melons 0.1 2) oats 0.1 2) peas 0.1 2) potatoes 0.1 2) pumpkins 0.1 2) strawberries 0.1 2) sugar beets 0.1 2) turnips 0.1 2) wheat 0.1 2) Cyprus citurs fruit 20 grapes 20 pome fruit 20 potatoes 20 stone fruit 20 vegetables 20 Denmark general 4) 28 European carrots 0 Community 5) other crops 0.4 Finland fodder crops 0.4 7) food crops 0.4 7) fruit 35 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) France beets 21 carrots 0 6) cereals 21 fruit 21 0.4 6) grapes 21 vegetables (excl. 0.4 6) carrots) Germany, berry fruit (excl. 21/28 8) Federal Republic strawberries) brassicas (excl. 21 cabbage) cabbage 14/21 8) 0.5 3) carrots 21 cereals 21 0.2 3) currants 2.0 3) field beans 21 0.5 3) fodder beets 28 fruiting vegetables 4 grapes 42/60 8) 2.0 3) hops 21 0.05 3) legume vegetables (excl. 7 0.5 3) field beans) lettuce 14 leafy vegetables 14 0.5 3) peaches 28 1.0 3) plums 28 1.0 3) pome fruit 28 1.0 3) potatoes 14/21 8) 2.0 3) root vegetables 21 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) stem vegetables 14 0.5 3) stone fruit 28 0.5 3) sugar beets 28 0.1 3) tobacco 7 vegetables (excl. 0.5 3) carrots) other fruit 0.5 3) other food crops 0.05 3) Great Britain apples, apricots, beans, blackberries, brassicas, carrots, celery, cereals (excl. barley and wheat) cherries, cucumbers (under glass), currants (black, red and white), fodder beets, gooseberries, lettuce (under glass), log anberries, mangels, nuts, parsnip, peaches, Dears, Deas, plums (incl. damsons), potatoes, raspberries, strawberries, sugar beets,, tomatoes (under glass) 21 barley, pastures, wheat 14 fodder beets (silage), mangels (silage) 10 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) India coffee, cotton 25 mangoes, peanuts 30 Israel almonds, apples, beans, brassicas, citrus fruit, cotton, cucumbers, eggplants, fruit, grapes, melons, peas, peppers, potatoes, pumpkins, sugar beets, tomatoes, zucchinis 21 Italy carrots 20 fruit 20 0.4 9) vegetables (excl. 20 0.4 9) carrots) Japan apples 30 Luxembourg 5) carrots 0.05 cereals 0.2 currants 2.0 grapes 2.0 plums 1.0 pome fruit 1.0 potatoes 0.2 vegetables (excl. 0.5 carrots) other fruit 0.5 other food crops 0.05 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) Mexico alfalfa 14/21 8) 5.0 apples 30 1.0 beans (green) 21 0.5 broccoli 7 1.0 Brussels sprouts 24 cabbage 7 1.0 cantaloupes 14 0.3 cauliflowers 7/14 8) chick peas 21 0.3 chilli 14 citrus fruit 30 cucumbers 14 1.0 eggplants 7/14 8) 1.0 grades 30/90 8) 0.1 kale 24 lettuce 14 2.0 maize 7/14 8) 0.5 melons (excl. 14 watermelons ) onions 30 0.05 oranges 7 1.0 pears 30 0.3 pecans 30 0.3 peppers 0.75 plums 30 potatoes 7 0.1 pumpkins 14 1.0 safflowers 7 1.0 sorghum 45 0.75 strawberries 14 2.0 watermelons 7 0.3 zucchinis 14 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) Netherlands beans 28 0.4 6) blackberries 28 broccoli 28 0.4 6) Brussels sprouts 28 0.4 6) cauliflowers 28 0.4 6 ) cereals 28 0.1 6) cherries 28 curr ants 28 kale 28 peaches 28 peas 28 0.4 6) plums 28 potatoes 28 0.05 6) r aspb err i es 28 small fruit (field grown) 28 0.4 6) strawberries 28 Pakistan chilli 60 rape (oilcake) 60 Portugal field crops 35 fruit (incl. 35 strawberries) pastures 14 potatoes 35 vegetables 35 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) South Africa apples 21 0.4 6) apricots 0.4 6) beans 10 0.2 6) Brussels sprouts 14 0.2 6) cabbage 14 0.2 6) cauliflowers 14 0.2 6) citrus fruit 21 0.5 6) cottonseed 0.1 6) cucurbits 21 eggplants 0.2 6) maize (green) 0.2 6) olives 0.1 6) onions 0.1 6) peaches 21 0.4 6) peanuts 0.1 6) pears 21 0.4 6) peppers 0.2 6) plums 0.4 6) potatoes 21 0.2 6) rooibos tea 0.1 6) sorghum 0.2 6) tomatoes 21 0.2 6) wheat 0.2 6) other Cruciferae 10 0.2 6) Spain 5) beets 30 carrots 0 cereals 30 cotton 30 fruit 30 0.4 vegetables (excl. carrots) 0.4 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) Sweden 6) bran 0.2 cereals 0.2 flour (cereals) 0.1 fruit 0.4 oat flakes 0.1 potatoes 0.2 vegetables 0.4 wheat flakes 0.1 Switzerland fruit (excl. cherries) 42 0.4 9) sugar beets 42 0.4 9) Taiwan apples 30 Thailand bananas, citrus fruit, coffee, cotton, grapes, maize, mung beans, peanuts, potatoes, rice, sorghum, soybeans, sugar- cane, tea, tobacco, vegetables 28-30 USA alfalfa 21 alfalfa, chaff and 11.0 hay (grown for seed) alfalfa, green 5.0 apples 1.0 beans 21 blackberries 7 2.0 broccoli 7 1.0 Brussels sprouts 3 1.0 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) cabbage 7 1.0 cauliflowers 7 clover 21 clover, chaff and 11.0 hay (grown for seed) clover, green 5.0 cotton 14 cotton seed 0.1 cucumbers 1.0 eggplants 7 1.0 filberts 105 0.05 grapes 90 0.1 lemons 7 1.0 lettuce 14/28 10) 2.0 lettuce 21 11) 2.0 lima bean forage 2.0 lima beans 0.5 maize (field-, sweet-, 7 corn, popcorn, grain and forage) maize (fodder and forage) 3.0 maize, grain (incl. 0.5 fresh corn, sweet corn, kernels and cob) melons 14 0.3 mint 14 mint hay 12.5 onions, dry bulb 0.05 onions (span.) 30 oranges 7 1.0 peppers 0.75 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) pea forage 21 2.0 pea hay 21 8.0 pears 30 0.3 peas 21 0.3 plums 35 1.0 potatoes 7 0.1 prunes 35 pumpkins 14 0.3 raspberries 7 2.0 safflower 7 1.0 snap bean forage 2.0 snap beans 0.5 sorghum (milled 2.0 fraction except flour) sorghum forage 21 2.0 sorghum grain 45 0.75 spearmint 14 strawberries 3 sugar beets 30 0.3 sugar beet tops 30 0.5 summer squash 1 1.0 turnips 7 0.3 turnip tops 21 2.0 walnuts 30 0.3 winter squash 14 0.3 meat, fat and meat-by- 0.01 products of cattle, goats, horses, pigs and sheep milk 0.01 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) Yugoslavia field crops 28 fruit 28 0.5 6) grapes 28 hops 28 sugar beets 28 0.5 6) other food crops 0.05 6) 1) = Demeton including demeton-O, demeton-S, demeton-O-methyl, demeton-S-methy and oxydemeton-methyl 2) = Level at or about the limit of determination 3) = Sum of oxydemeton-methyl, demeton-S-methyl and demeton-S-methyl sulphone expressed as demeton-S-methyl 4) = No application to crops with a short vegetation period 5) = Sum of oxydemeton-methyl, demeton-S-methyl and demeton-S-methyl sulphone separately calculated or expressed as demeton-S-methyl 6) = Sum of oxydemeton-methyl, demeton-S-methyl and demeton-S-methyl sulphone 7) = Preliminary 8) = Depending on formulation 9) = Sum of oxydemeton-methyl and demeton-S-methyl sulphone separately calculated or expressed as demeton-S-methyl sulphone 10) = In California and Arizona, depending on application rate 11) = In other States Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) demeton-S-methyl sulphone (in "Gusathion MS") Austria 1) cereals 0.2 fruit 0.4 potatoes 0.2 sugar beets 0.4 vegetables (excl. 0.4 carrots) other crops 0.05 Belgium 1) carrots 0 fruit 42 fruit (excl. citrus) 0.4 vegetables (excl. 0.4 carrots) Brazil 1) apples 1.0 barley 0.2 cotton 0.1 cucumbers 0.2 eggplants 0.2 maize 0.2 melons 0.2 oats 0.2 peaches 1.0 pears 0.5 plums 1.0 potatoes 0.2 pumpkins 0.2 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) quinces 0.5 rice 0.2 rosemallow 0.05 rye 0.2 sorghum 0.2 tomatoes 0.5 watermelons 0.2 wheat 0.2 eggs (shell-free) 0.05 2) meat 0.05 2) milk 0.05 2) Denmark carrots 0.05 2) cereals (raw) 0.2 fruit 0.5 grapes 0.5 potatoes 0.2 vegetables (excl. 0.5 carrots) other root crops 0.5 animals fat 0.05 2) eggs 0.05 2) meat 0.05 2) milk 0.05 2) milk products 0.05 2) European carrots 0 Community 3) other crops 0.4 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) France beets 21 carrots 0 4) fruit 21 0.4 4) grapes 21 pot atos 21 vegetables (excl. 0.4 4) carrots) Germany, cereals 0.2 1) Federal Republic cherries 28 0.5 1) currants 2.0 1) grapes 49 2.0 1) peaches 1.0 1) plums 35 1.0 1) pome fruit 28 1.0 1) potatoes 0.2 1) prunes 35 sugar beets 0.1 1) vegetables (excl. 0.1 1) carrots) other fruit 0.5 1) other food crops 0.05 1) Italy apples 35 beets 35 carrots 0 3) citrus fruit 35 fruit 0.4 3) grapes 35 peaches 35 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) pears 35 potatoes 35 vegetables (excl. 35 0.4 3) carrots) Luxembourg 5) carrots 0.05 cereals 0.2 currants 2.0 grapes 2.0 plums 1.0 pome fruit 1.0 potatoes 0.2 vegetables (excl. 0.5 carrots) other fruit 0.5 other food crops 0.05 Netherlands 4) beans 0.4 berry fruit (field grown) 0.4 brassicas 0.4 cereals 0.05 peas 0.4 potatoes 0.05 Portugal apples 21 citrus fruit 91 pastures 14 pears 21 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) South Africa 4) apples 0.4 apricots 0.4 beans 0.2 citrus fruit 0.5 cottons eed 0.1 cruciferae 0.2 eggplants 0.2 maize (green) 0.2 olives 0.1 onions 0.1 peaches 0.4 peanuts 0.1 pears 0.4 peppers 0.2 plums 0.4 potatoes 0.2 rooibos tea 0.1 sorghum 0.2 tomatoes 0.2 wheat 0.2 Spain carrots 0 3) cotton 28 fruit 0.4 3) pome fruit 28 0.4 3) stone fruit 28 0.4 3) vegetables (excl. 0.4 3) carrots) Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) Sweden 4) bran 0.2 cereals 0.2 flour (cereals) 0.2 fruit 0.4 oat flakes 0.1 potatoes 0.2 vegetables 0.4 wheat flakes 0.1 Switzerland fruit 42 0.4 6) sugar beets 42 0.4 6) USA alfalfa, chaff 11.0 and hay (for seed) alfalfa, green 5.0 apples 1.0 blackberries 2.0 broccoli 1.0 Brussels sprouts 1.0 cabbage 1.0 cauliflower 1.0 clover, chaff and 11.0 hay (grown for seed) clover, green 5.0 cottons eed 0.1 cucumbers 1.0 eggplants 1.0 filberts 0.3 grapefruit 1.0 grapes 0.1 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) lemons 1.0 lettuce, head 2.0 lima bean forage 2.0 lima beans 0.5 maize, fodder and 3.0 forage maize, grain (incl. 0.5 fresh corn, sweet corn, kernels and cobs) melons 0.3 mint hay 12.5 onions, dry bulb 0.05 oranges 1.0 pea forage 2.0 pea hay 8.0 pears 0.3 peas 0.3 peppermint (dried) 12.5 peppers 0.75 plums (fresh prunes) 1.0 potatoes 0.1 pumpkins 0.3 raspberries 2.0 safflower 1.0 snap bean foraoe 2.0 snap beans 0.5 sorghum forage 2.0 sorghum, grain 0.75 sorghum (milled 2.0 fraction except flour) squash, summer 1.0 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) squash, winter 0.3 strawberries 2.0 sugar beets 0.3 sugar beet tops 0.5 turnips 0.3 turnip tops 2.0 walnuts 0.3 meat, fat and 0.01 meat by-products of cattle, goats, horses, pigs and sheep milk 0.01 Yugoslavia 4) fruit 0.5 sugar beets 0.5 other food crops 0.05 1) = Sum of demeton-S-methyl sulphone, demeton-S-methyl and oxydemeton-methyl expressed as demeton-S-methyl 2) = Level at or about the limit of determination 3) = Sum of demeton-S-methyl sulphone, demeton-S-methyl and oxydemeton-methyl separately calculated or expressed as dEmeton-S-methyl sulphone 4) = Sum of demeton-S-methyl sulphone, demeton-S-methyl and oxydeaeton-methyl 5) = Sum of demeton-S-methyl sulphone, demeton-S-methyl and oxydemeton-methyl separately calculated or expressed as demeton-S-methyl 6) = Sum of demeton-S-methyl sulphone and oxydemeton-methyl separately calculated or expressed as demeton-S-methyl sulphone Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) Demeton-S-methyl Australia 1) cereals 21 0.5 cotton 21 field crops 21 herbs 0.5 hops 21 0.5 macadamia nuts 0.05 2) oil seed 0.5 pastures 3 pome fruit 21 0.5 potatoes 21 rape 21 root crops 21 stock food 3 stone fruit 21 0.5 strawberries 0.5 tobacco 21 tomatoes 21 0.5 vegetables 21 0.5 water 0.03 Austria cereals 35 0.4 3) field crops 35 fruit 35 0.4 3) grapes 35 0.05 3) potatoes 35 0.2 3) sugar beets 35 0.4 3) vegetables (excl. 35 0.4 3) carrots) Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) other registered 0.05 3) crops Belgium beets 28 carrots 28 0 3) fruit (excl. citrus) 28 0.4 3) hops 28 pastures 10 potatoes 28 0.1 3) vegetables (excl. 28 0.4 3) carrots) Brazil 1) apples 21 1.0 barley 21 0.2 cotton 14 0.2 cucumbers 21 0.2 eggpl ants 21 0.2 maize 21 0.2 melons 21 0.2 oats 21 0.2 peaches 21 1.0 pears 21 0.5 plums 21 1.0 potatoes 7 0.2 pumpkins 21 0.2 quinces 21 0.5 rice 21 0.2 rosemallow 21 0.05 rye 21 0.2 sorghum 21 0.2 tomatoes 21 0.5 wheat 21 0.2 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) eggs (shell-free) 0.05 2) meat 0.05 2) milk 0.05 2) France carrots 0 6) fruit 0.4 6) vegetables (excl. 0.4 6) carrots) Germany, cereals 0.2 3) Federal Republic currants 2.0 3) fodder beets 28 grapes 2.0 3) peaches 1.0 3) plums 1.0 3) pome fruit 1.0 3) potatoes 14 2.0 3) sugar beets 28 0.1 3) vegetables (excl. 0.5 3) carrots other fruit 0.5 3) other food crops 0.05 3) Great Britain apples, apricots, beans, beetroot, blackberries, brassicas, carrots, celery, cereals (excl. barley and wheat), cherries, cucumbers (under glass), currants Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) (black, red and white), fodder beets, goose- berries, lettuce (field grown, and under glass), loganberries, mangels, nuts, parsnip, peaches, Dears, peas, plums, potatoes, raspberries, strawberries, sugar beets, tomatoes (under glass) 21 barley, pastures, wheat 14 fodder beets (silage), 10 mangels (silage) Hungary general 30 0.5 Israel apples 1.0 blueberries 2.0 beans 0.2 brassicas 0.2 broccoli 0.2 cereals 0.2 citrus fruit 0.5 cottons eed 0.1 eggplants 0.2 fodder 5.0 forage 10.0 grapes 2.0 lettuce 0.5 peaches 1.0 pears 0.5 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) peas 0.2 peppers 0.2 plums 1.0 potatoes 0.2 pumpkins 0.2 strawberries 0.5 sugar beets 0.1 tomatoes 0.2 zucchinis 0.5 eggs (shell-free) 0.05 meat and fat of 0.05 cattle, pigs, poultry and sheep milk 0.05 milk products 0.05 Italy carrots 20 0 4) fruit 20 0.4 4) vegetables (excl. 20 0.4 4) carrots ) Luxembourg 7) carrots 0.05 cereals 0.2 currants 2.0 grapes 2.0 plums 1.0 pome fruit 1.0 potatoes 0.2 vegetables (excl. 0.5 carrots) Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) other fruit 0.5 other food crops 0.05 Netherlands 5) beans 0.4 berry fruit (field grown) 0.4 brassicas 0.4 cereals 0.5 peas 0.4 potatoes 0.05 New Zealand alfalfa 7 apples 21/35 8) broad beans 21/35 8) Brussels sprouts 21/35 8) cabbage 21/35 8) cauliflower 21/35 8) cereals 21/35 8) cocksfoot 21/35 8) currants 21/35 8) (red and black) marrow stemmed 21/35 8) pastures 14 pears 21/35 8) potatoes 21/35 8) rape 21/35 8) raspberries 21/35 8) strawberries 21/35 8) turnips 21/35 8) Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) Norway berry fruit 28 9) cereals 28 9) pome fruit 28 9) Peru citrus fruit 28 cucurbits 28-42 wheat 14 Poland apples, carrots, cauliflower, cherries (excl. early species), curly kale, dill, mustard, peaches, pears, peas, plums, raspberries, rutabagas, spinach, strawberries 42 0.4 carrots (animal feed), field beans, fodder beets, hops, peas (animal feed), potatoes, rape, sugar beets, tobacco 42 fruit, vegetables 0.4 South Africa 5) apples 21 0.4 apricots 21 0.4 beans 10 0.2 citrus fruit 0.5 cotton (as feed stuff) 21 0.1 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) cotton (harvest) 5 cruciferae 10-14 0.2 eggplants 21 0.2 maize 21 0.2 maize (green) 0.2 olives 90 0.1 onions (green) 21 0.1 peaches 21 0.4 peanuts 21 0.1 pears 21 0.4 peas 21 peppers 14 0.2 plums 21 0.4 potatoes 21 0.2 rooibos tea 0.1 sorghum 21 0.2 tomatoes 21 0.2 wheat 21 0.2 Spain 4) carrots 0 fruit 0.4 vegetables (excl. 0.4 carrots) Sweden 5) bran 0.2 cereals 28 0.2 flour (cereals) 0.1 fruit (incl. 28 0.4 berry fruit) oat flakes 0.1 Table 10. (continued) Country Crop/Commodity Safety MRL intervals (mg/kg) (days) potatoes 28 0.2 vegetables (incl. 28 0.4 root vegetables) wheat flakes 0.1 Yugoslavia 5) fruit 0.5 sugar beets 0.5 other food crops 0.05 RECOMMENDATIONS The following maximum residue levels are recorded as suitable for use as guideline levels. GL Interval on which (mg/kg) GLs are based (days) cherries 1 35 bulb vegetables 0.1 21 brassica leafy vegetables 0.2 21 tomatoes 0.2 3 peppers 1 14 cereal grains 0.2 (replacing "raw cereals" at the same level) REFERENCES Hill, A.R.C., Wilkins, J.P.G. Findlay Nina, R.I. and Lontay Karen E.M. 1984 Organophosphorus sulphides, sulphoxides and sulphones. Part 1. Determination of Residues in Fruit and Vegetables by Gas- Liquid Chromotography. Analyst 109 483. Houseworth, L.D., Tweedy, B.G. : The metabolism of METASYSTOX-R in 1974 soil. Mobay Report No. 39219. Nichols, S.S., Thornton, J.S. Photodecomposition of METASYSTOX-R in 1978 aqueous solution and on silt loam soil. Mobay Report No. 54412. Phul, R.J., Hurley, J.B. The aerobic and anaerobic soil metabolism of 1978 METASYSTOX-R. Mobay Report No. 63056. Shaw, H.R., II: Determination of soil-bound residues and uptake by 1975 rotational crops from soil treated with METASYSTOX-R. Mobay Report No. 43971, (revised, April 11, 1975). Thornton, J.S. The effects of feeding METASYSTOX-R to chickens. Mobay 1975 Report No. 46081. Thornton, J.S., Hurley, J.B., Obrist, J.J.: Soil thin-layer mobility 1976 of twenty-four pesticide chemicals. Mobay Report No. 51016. Wagner, K., Oehlmann, L. Metabolism of demeton-S-methyl sulphone in 1980 soil. Bayer AG, PF-A/CE-MR unpublished Report RA-170. Wilmes, R. Orientating Studies on Stability to Light. Bayer AG, PF-A/ 1982 CE-PIQ-ENA. Ziegler, W., Engelhardt, G. Wallnofer, P.R., Oehlmann, L. Wagner, K. 1980 Degradation of Demeton-S-Methyl Sulphoxide (Metasystox R) by Soil Micro-organisms. J. Agric. Food Chem. 28, 1102 - 1106.
See Also: Toxicological Abbreviations Demeton-S-methyl and related compounds (WHO Pesticide Residues Series 3) Demeton-S-Methyl and Related Compounds (Pesticide residues in food: 1989 evaluations Part II Toxicology)