PESTICIDE RESIDUES IN FOOD - 1982 Sponsored jointly by FAO and WHO EVALUATIONS 1982 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, 23 November - 2 December 1982 Food and Agriculture Organization of the United Nations Rome 1983 CYPERMETHRINExplanation Cypermethrin was reviewed by the JMPR in 1979 and 19811/ and MRLs were recommended on a wide range of crops and on meat and milk products. Further data requested by the 1981 Meeting included residue data on soybeans from trials carried out in the U.S. and on residues in poultry and poultry products derived from feeding treated produce. Data on these requested items, as well as those on a number of other crops for which no MRL has yet been proposed, have been evaluated. RESIDUES IN FOOD AND THEIR EVALUATION USE PATTERN Preharvest Recommendations for use of cypermethrin on the crops not previously evaluated by the JMPR, or for which additional data were requested, are summarized in Table 1. Where several applications become necessary due to pest pressure, it is unlikely that the frequency of treatment would be more often than twice a month. RESIDUES RESULTING FROM SUPERVISED TRIALS Soybeans A series of trials were carried out in the U.S. using aerial applications of 9-45 l/ha, or ground applications of 90-360 l/ha, and a standard rate of 110 g a.i./ha. 1/ See Annex 2 for FAO and WHO documentation. Table 1. Recommended Uses of Cypermethrin Application Minimum Preharvest Crops Pest Rate (g/ha) interval Soybean (USA) Pseudoplusia includens 50 - 100 3-4 weeks Trichoplusia ni Anticarsia gemmatalis Nezara viridula Plattypena scabra Epilachna verivestis Heliothis armigera Laphyma exigua Leeks Acrolepia assectella 30 - 60 7 days Phytobia cepae Thrips tabaci Onions (bulb) Acrolepia ascectella 38 - 70 3 days Carrots Agrotis segetum 25 - 70 7 days Turnips Auxoa nigricans Swedes (Rutabagas) Parsnips Phaseolus spp. Sitona spp. 25 - 60 7 days Aphis fabae Viola spp. Spinach Trialeurodes spp. 25 - 60 7 days Black currant Nematus olfaciens 40 Pteronidea ribesii 25 g/ha low volume Gooseberries Lygocoris pabulinus or 0.005% high 7-14 days Aphis spp. volume Sunflowers Desmoris constructus Agrotis spp. Euxoa spp. Spodoptera spp. 75 7 days Linseed Homoeosoma electellum Thripidae Agrotis ipsilon Table 1. Recommended Uses of Cypermethrin Application Minimum Preharvest Crops Pest Rate (g/ha) interval Groundnuts Aphis craccivora 75 7 days Spodoptera spp. Thripidae Barley Macrosiphum avenae 25 - 50 4 weeks Mushrooms Megaselia spp. 6 mg/m2 1-2 days Sciara spp. The trials encompassed a representative range of the southern and mid-western soybean-growing states. With one exception, the treated crops were harvested 21-31 days after the second spray application. The residues data and trials details are summarized in Table 2 (Ussary 1982). There was no obvious difference in the cypermethrin levels in the beans at harvest following either ground or aerial application. In all cases, the residue levels were less than the MRL of 0.05 mg/kg recommended by the 1979 Meeting for soybean. Leek Typically, good agricultural practice requires the application of 30-60 g/ha and a minimum treatment to harvest interval of 7 days. A trial was conducted in The Netherlands in 1981. A 10% formulation was applied to four replicate plots at 30 g a.i./ha. Samples of whole plants were taken from each plot for analysis at intervals up to 14 days after spraying and the residues determined. Cypermethrin levels of 0.17-0.21 mg/kg on the day of spraying declined to 0.05-0.06 mg/kg after 7 days and to 0.02-0.04 mg/kg after 14 days. Additional trials were carried out in Germany in which 3 applications were made at 60 g/ha. The data are summarized in Table 3 (Swaine et al 1982a; Shell Chimie S.A. 1979, 1980). Following recommended treatments, residues of cypermethrin in leeks at 7 days after treatment are likely to occur at a level exceeding 0.5 mg/kg. Table 2. Cypermethrin Residues in Soybeans, U.S., 19811/ Interval Cypermethrin Rate of Volume between Last Levels Method of application of Spray Number of Application and Determined Location application (g a.i./ha) (l/ha) Applications harvest (days) (mg/kg) Georgia Aerial 110 45 2 24 ND Missouri Aerial 110 27 2 21 0.01 Alabama Aerial 110 9 2 21 Trace (<0.01) Alabama Aerial 110 9 2 21 ND Louisiana Aerial 110 9 2 21 0.01 Missouri Aerial 110 45 2 31 0.01 Arkansas Aerial 110 9 1 30 0.02 Illinois Ground 110 180 2 21 0.01 Missouri Ground 110 90 2 29 0.04 Florida Ground 110 330 2 21 Trace (<0.01) Maryland Ground 110 360 2 25 0.01 North Carolina Ground 110 250 2 1 0.01 Table 2. (con't) Interval Cypermethrin Rate of Volume between Last Levels Method of application of Spray Number of Application and Determined Location application (g a.i./ha) (l/ha) Applications harvest (days) (mg/kg) South Dakota Ground 110 90 2 21 0.03 Minnesota Ground 110 245 2 21 0.02 1/ Following either ground or aerial applications of 36% EC formulations. All figures are corrected for % recovery. ND means not detected, less than 0.01 mg/kg. Bulb Onions Residues data have been obtained from trials in Canada in which applications up to the excessively high rate of 2 g/ha were used. In all cases, in spite of the high rates sometimes employed, cypermethrin was not found in the bulbs (limit of determination 0.01 mg/kg). These trials and the resulting data are also included in Table 3 (Swaine et al 1980d, 1981a) Root and Tuber Vegetables Residue experiments have been carried out on carrots in the U.K., Canada and Germany. Dose rates up to 7 g/ha were applied and as many as 8 treatments were used. In all cases, residues were below 0.05 mg/kg, even at zero treatment to harvest interval. Trials have also been carried out with parsnips and swedes in the U.K. where application rates of 25 and 50 g/ha were used 48 and 5 days prior to harvest. Residue levels in the roots were 0.01 mg/kg or less. These trials are summarized in Table 4 (Swaine et al 1980a; Shell Chimie S.A. 1980, 1981; Shell Research Ltd. 1981). Spinach Trials were conducted on spinach in Germany and the U.K., in which cypermethrin was applied at 5 g/ha and also at the somewhat high rate of 100 g/ha. A description of the trials and the results are given in Table 5 (Swaine et al 1981c; Shell Chimie S.A. 1981). When used according to good agricultural practice, cypermethrin is unlikely to give rise to residue levels on spinach above 2 mg/kg. Beans Although the 1979 JMPR evaluated data for beans (Phaseolus), these were only for dried beans without pods. Data are now available for green Phaseolus beans in pod and Vicia beans without pod from the trials summarized in Table 6 (Swaine et al 1981b; Shell Chimie S.A. 1980, 1981; Shell Research Ltd. 1980). Residue levels of cypermethrin in whole Phaseolus beans (including pods) were all below 0.5 mg/kg following use of the product as recommended. Residues in Vicia beans, following removal from the pods as for normal consumption, were below the limit of determination of 0.01 mg/kg one week or more after treatment. Table 3. Cypermethrin Residues in Leeks and Onions Dose Spray Applications Preharvest Rate Rate Interval Residues Crop Country Variety Formulation (g/ha) (l/ha) No. Interval (days) (mg/kg) Leeks Netherlands Triomfator 10% EC 30 1 000 1 0 0.18,0.17,0.17,0.21 3 0.07,0.09,0.08,0.09 7 0.05,0.06,0.05,0.06 14 0.04,0.04,0.03,0.02 Leeks Germany Siegfried 10% EC 60 3 2 weeks 0 0.44 7 0.24 14 0.12 21 0.01 28 <0.01 60 3 2 weeks 0 0.60 7 0.39 14 0.03 21 0.02 28 <0.01 60 3 2 weeks 0 0.55 7 0.25 14 0.07 21 0.02 28 <0.01 Onion Canada Garnet 40% EC 70 450 4 2 weeks 7 <0.01,<0.01,<0.01,<0.01 Onion Canada Exporter 40% EC 50 450 7 10-12 days 3 0.05,0.08,0.07,0.06 7 <0.01,<0.01,<0.01,<0.01 Table 3. (cont'd) Dose Spray Applications Preharvest Rate Rate Interval Residues Crop Country Variety Formulation (g/ha) (l/ha) No. Interval (days) (mg/kg) Onion Canada 25% EC 35 250 1 64 <0.01 70 250 1 64 <0.01 70 340 1 10 <0.01 70 340 1 19 <0.01 140 340 1 10 <0.01 140 340 1 19 <0.01 280 340 1 10 <0.01 280 340 1 19 <0.01 Onion Canada 25% EC 200 250 1 60 <0.01 Table 4. Cypermethrin Residues in Root and Tuber Vegetables Dose Spray Applications Preharvest Residues Rate Rate Interval Crop Country Variety Formulation (g/ha) (l/ha) No. Interval (days) (mg/kg) Carrot UK Breeders 10% EC 25 600 1 48 0.01 Berjo 50 1 48 0.01 Carrot Canada Spartan 40% EC 50 450 7 9-13 days 3 <0.01,<0.01,<0.01,<0.01 Fancy <0.01,<0.01,<0.01,<0.01 Carrot Canada Spartan 40% EC 70 400 8 12-18 days 7 0.02 Fancy 14 0.03 Carrot Germany Nantaise 10% EC 60 500 3 2 weeks 0 <0.01 7 <0.01 14 <0.01 21 <0.01 Gonsenheimer 10% EC 60 500 3 2 weeks 0 0.02 7 <0.01 14 <0.01 21 <0.01 Hilds Fanal 10% EC 60 500 3 2 weeks 0 0.04 7 <0.01 14 <0.01 21 <0.01 Table 4. (con't) Dose Spray Applications Preharvest Residues Rate Rate Interval Crop Country Variety Formulation (g/ha) (l/ha) No. Interval (days) (mg/kg) Parsnip UK Alba 10% EC 25 600 1 48 <0.01 50 600 1 48 <0.01 Swede UK 10% EC 25 600 2 5 <0.01 50 600 2 5 0.01 Table 5. Cypermethrin Residues in Spinach Dose Spray Applications Preharvest Rate Rate Interval Interval Residues Country Variety Formulation (g/ha) (l/ha) No. (weeks) (days) (mg/kg) UK Bloomsdale 10% EC 100 500 1 0 5.7 3 1.8 7 1.2 14 0.19 Germany Monnopa 10% EC 60 500 3 2 0 0.79 7 0.13 14 0.05 21 <0.01 Monnopa 10% EC 60 500 3 2 0 2.00 7 0.49 14 0.10 21 0.01 Matares 10% EC 60 500 3 2 0 3.30 7 0.75 14 0.06 21 0.02 Table 6. Cypermethrin Residues in Beans Dose Spray Applications Preharvest Rate Rate Interval Residues Crop Country Variety Formulation (g/ha) (l/ha) No. Interval (days) (mg/kg) Dwarf U.K. Carousel 10% EC 25 260 1 0 0.16, 0.01 Beans 50 260 1 0 0.59 Kidney France Mangetout 5% EC 50 1 000 1 14 0.05 Beans Green S. Africa Gallatin 20% EC 0.003% 700- 6 10-12 days 7 0.13 Beans 1 700 14 0.07 Green Fed. Rep. of Beans Germany Perle v. 10% EC 60 3 2 weeks 0 0.75 Marbach 3 0.53 5 0.25 7 0.20 10 0.15 Weis Reising 10% EC 60 500 3 2 weeks 0 0.40 3 0.30 5 0.25 7 0.20 10 0.10 Table 6. (con't) Dose Spray Applications Preharvest Rate Rate Interval Residues Crop Country Variety Formulation (g/ha) (l/ha) No. Interval (days) (mg/kg) Green Fed. Rep. of beans Germany Marga 10% EC 60 500 3 2 weeks 0 0.76 3 0.51 5 0.41 7 0.28 10 0.15 Pearle v. 10% EC 60 500 3 2 weeks 0 0.21 Marbach 3 0.15 (glasshouse) 5 0.12 7 0.14 10 0.11 Hild Neckar 10% EC 60 500 3 2 weeks 0 0.57 Konigin 3 0.50 5 0.30 7 0.24 10 0.15 Marga 10% EC 60 500 3 2 weeks 0 0.61 3 0.58 5 0.49 7 0.33 10 0.24 Broad U.K. Triple White 21 600 1 18 <0.01 Beans 21 600 2 8 days 10 <0.01 Field U.K. Maris Bead 25 500 1 0 0.09 Beans Table 6. (con't) Dose Spray Applications Preharvest Rate Rate Interval Residues Crop Country Variety Formulation (g/ha) (l/ha) No. Interval (days) (mg/kg) Broad France 5% EC 50 1 000 1 8 <0.01 Beans 15 <0.01 31 <0.01 D'Aquadulce 5% EC 50 1 000 1 7 <0.01 13 <0.01 28 <0.01 Currants and Gooseberries Residue trials were carried out in the U.K. on black currants and gooseberries and in the Federal Republic of Germany on red currants. These are summarized in Table 7 (Swaine et al 1980b; Shell Chimie S.A. 1978, 1980; Shell Research Ltd. 1980). Cypermethrin residues in the whole fruit did not exceed 0.5 mg/kg even on the day of treatment. Oilseeds (Sunflowers and Linseed) Details of experiments carried out on sunflower and linseed are summarized in Table 8 (Sobolewski 1981; Shell Chimie 1981, 1982; Robertson 1980; Shell Research Ltd. 1980). Trials with sunflowers have been carried out in Australia, Argentina, Canada and South Africa using a wide range of application rates. Residue levels observed in seeds were all at or below 0.1 mg/kg, while those in whole heads were below 0.2 mg/kg from normally recommended treatments. Two trials on linseed were carried out in Canada using 28 g a.i./ha on up to 3 occasions with a minimum PHI of 4 weeks. Residue levels reported were all 0.05 mg/kg or less. Peanuts Trials have been carried out in Canada, India and South Africa using dose rates up to 100 g a.i./ha applied 7 days or more before harvest. In no instance was residues found at a limit of determination of 0.01 mg/kg (Table 9) (Shell Chimie S.A. 1980, 1981, 1982). Barley Residue experiments were carried out in Europe and Canada using dose rates up to 62 g a.i./ha on 1 to 3 occasions. Residue levels in whole (unhusked) barley grain from crops treated according to good agricultural practice were all below 0.5 mg/kg where treatments were made 3-4 weeks prior to harvest (Table 10) (Swaine et al 1980c, 1982d; Shell Research Ltd. 1981). Mushrooms (Agaricus bisporus) Cypermethrin is used as a spray, fog or smoke treatment in mushroom houses. Because of the need to re-treat frequently and the continuous cropping of mushrooms that takes place over an extended period, an interval of 1-2 days between an application and cropping is frequently necessary. In a trial in The Netherlands in 1981, a 10% EC formulation was applied twice at rates of 60, 120 and at the exceptionally high rate of 240 g a.i./ha. Replicate samples of mushrooms were taken for analysis 1, 2 and 3 days after the second spray. The cypermethrin levels found are summarized in Table 10 (Swaine et al 1982b). Table 7. Cypermethrin Residues in Currants and Gooseberries Dose Spray Preharvest Rate Rate Interval Residues Crop Country Variety Formulation (g/ha) (l/ha) (days) (mg/kg) Black currant U.K. Baldwin 10% EC 25 1 100 0 0.18 25 1 100 1 0.13 25 1 100 3 0.15 25 1 100 7 0.12 25 1 100 14 0.07 50 1 100 7 0.23 Baldwin 25 1 100 7 0.11 50 1 100 7 0.10 Westwick 25 1 100 7 0.15 Choice 50 1 100 7 0.29 Black currant U.K. Baldwin 10% EC 37.5 1 100 2 0.04 7 0.06 Black currant U.K. Baldwin 10% EC 37.5 1 500 2 0.13 7 0.21 Red currant1/ Fed. Rep. of Germany Red Lake 10% EC 0.01% 1 500 0 0.40 7 0.35 14 0.29 21 0.20 Table 7. (con't) Dose Spray Preharvest Rate Rate Interval Residues Crop Country Variety Formulation (g/ha) (l/ha) (days) (mg/kg) Gooseberry U.K. Careless 5% EC 0.005% 24 0.03 Gooseberry U.K. Leveller 10% EC 25 1 100 7 0.13 25 1 100 7 0.05 25 560 9 0.09 50 1 100 7 0.21 50 1 100 7 0.12 1/ Two applications at an interval of 2 weeks. All others single applications. Table 8. Cypermethrin Residues in Oilseeds Spray Applications Dose Rate Rate Preharvest Residues Crop Country Variety Formulation (g/ha) (l/ha) No. Interval Interval (mg/g) Sunflower Australia Cargill 25% EC 75 315 2 16 days 0 days 0.06 Seeds Sun Ace 84 7 days 0.10 14 days 0.04 21 days 0.03 100 315 2 16 days 0 days 0.07 7 days 0.05 14 days 0.05 21 days 0.04 200 315 2 16 days 0 days 0.14 84 7 days 0.15 14 days 0.11 21 days 0.08 Sunflower Australia Hysum 31 20% EC 75 50 1 1 day 0.32 Heads 7 days 0.18 13 days 0.04 20 days 0.03 75 50 1 1 day 0.41 7 days 0.12 13 days 0.03 20 days 0.02 Sunflower Argentina Empire 25% EC 50 11 1 17 days 0.04 Seeds Table 8. (con't) Spray Applications Dose Rate Rate Preharvest Residues Crop Country Variety Formulation (g/ha) (l/ha) No. Interval Interval (mg/g) Sunflower Canada CSP8944 40% EC 14 118 1 10 weeks <0.01,<0.01,<0.01,<0.01 Seeds 20 118 1 10 weeks <0.01,<0.01,<0.01,<0.01 Sunflower Canada CMH103 40% EC 14 - 1 16 weeks <0.01,<0.01,<0.01,<0.01 Seeds 20 - 1 16 weeks <0.01,<0.01,<0.01,<0.01 16 weeks <0.01,<0.01,<0.01,<0.01 28 - 1 Sunflower S. Africa Sensako 20% EC 20 (by air) 1 1 day <0.01 seeds 5 days <0.01 8 days <0.01 12 days <0.01 26 days <0.01 Sensako 20% EC 30 (by air) 1 5 days <0.01 9 days <0.01 12 days <0.01 16 days <0.01 30 days <0.01 Table 8. (con't) Spray Applications Dose Rate Rate Preharvest Residues Crop Country Variety Formulation (g/ha) (l/ha) No. Interval Interval (mg/g) Linseed Canada Dufferin 40% EC 28 118 1 7 weeks <0.01,<0.01,<0.01,<0.01 (Seeds) 8 weeks <0.01,<0.01,<0.01,<0.01 12 weeks <0.01,<0.01,<0.01,0.01 Dufferin 40% EC 28 118 3 4 & 1 wk. 7 weeks 0.01,<0.01,0.01,0.02 Redwood 40% EC 28 118 1 4 weeks 0.04,0.05,0.05,0.02 6 weeks 0.02,0.02,0.03,0.03 10 weeks <0.01,<0.01,<0.01,<0.01 Redwood 40% EC 28 118 3 4 & 1,1/2 4 weeks 0.03,0.04,0.04,0.04 wks. Table 9. Residues of Cypermethrin in Peanuts Dose Spray Applications Preharvest Residues Rate Rate Country Variety Formulation (g/ha) (l/ha) No. Interval Interval (mg/kg) Canada Valencia 40% EC 50 225 2 6 weeks 6 weeks <0.01,<0.01,<0.01,<0.01 India TMV-9 10% EC 50 500 1 13 days <0.01 20 days <0.01 27 days <0.01 100 500 1 13 days <0.01 20 days <0.01 27 days <0.01 TMV-7 10% EC 50 500 1 14 days <0.01 21 days <0.01 28 days <0.01 100 500 1 14 days <0.01 21 days <0.01 28 days <0.01 TMV-7 10% EC 50 500 1 2 weeks <0.01 3 weeks <0.01 4 weeks <0.01 100 500 1 2 weeks <0.01 3 weeks <0.01 4 weeks <0.01 Table 9 (con't) Dose Spray Applications Preharvest Residues Rate Rate Country Variety Formulation (g/ha) (l/ha) No. Interval Interval (mg/kg) S. Africa 20% EC 10 1 7 days <0.01 12 days <0.01 25 days <0.01 15 1 7 days <0.01 12 days <0.01 25 days <0.01 Table 10 Cypermethrin Residues in Barley Grain Country Variety Formulation Dose Spray Applications Residues Rate Rate Pre-harvest (mg/kg) (g/ha) (l/ha) No. Interval Interval (days) (days) U.K. Sonya 10% EC 25 250 2 42 0.10 (Winter) 50 250 2 42 0.24 Sweden 6.25% 62.5 1 49 <0.01 Canada Klages 4% EC 28 118 1 26 0.22,0.30,0.27,0.22 42 0.13,0.15,0.12 66 <0.01,<0.01,<0.01,<0.01 28 118 3 24 & 16 26 0.47,0.37,0.27,0.51 Canada Bonanza 40% EC 28 118 1 25 0.08,0.16,0.16,0.18 32 0.11,0.16,0.16,0.08 48 0.03,0.02,0.04,0.03 28 118 3 16 & 7 25 0.25,0.25,0.22,0.16 Fed. Rep. of Germany Aura 10% EC 50 500 1 48 0.02 Aura 10% EC 50 500 1 53 0.03 Table 11. Cypermethrin Residues in Mushrooms Dose Spray Application Preharvest Residues Crop Country Variety Formulation Rate Rate No. Interval (mg/kg) (g/ha) (l/ha) (days) Mushrooms Netherlands Somycel 53 10% EC 60 10 000 2 1 0.02,0.03 2 0.01,0.01 3 0.01,<0.01 120 10 000 2 1 0.04,0.04 2 0,02,0.02 3 0.01,<0.01 240 10 000 2 1 0.08,0.07 2 0.04,0.03 3 0.02,0.02 At the two lower rates, cypermethrin levels were consistently below 0.05 mg/kg in mushrooms sampled during the period 1-3 days after the second application. FATE OF RESIDUES Data were reviewed by the 1979 Meeting on the fate of residues during peeling, extraction, wine making, cooking and oilseed processing. Additional data are now available on juice production, cooking and oilseed processing and confirm the conclusions of the 1979 Meeting. In Processing Black currants containing weathered residues of cypermethrin were processed through a laboratory simulation of the commercial process whereby black currant juice is extracted. On average, less than 0.5% of the original residue was transferred into the juice (Swaine et al 1981d). Cypermethrin levels in cabbage remained unchanged when samples were boiled for 15 minutes. No cypermethrin was detected in the water (limit of determination: 0.05 mg/kg) (Table 12) (Swaine et al 1982c). Table 12. Distribution of Cypermethrin Residues in Cabbage before and after Boiling Residue Fortification Total Residue Found (mg/kg)1 Sample (mg/kg) level Residue (mg/kg) (mg/kg) Cabbage Water 1 0.02 1.0 1.02 1.03 0.05 2 0.02 1.0 1.02 1.03 0.05 3 0.02 1.0 1.02 1.03 0.05 1 Limit of determination: 0.01 mg/kg (cabbage); 0.05 mg/kg (water) Two further cottonseed oil processing studies were conducted in the U.S. In 1979, samples of cottonseed were collected from a field trial 74 days after the last of eleven aerial applications of cypermethrin at approximately 70 g a.i./ha. In 1980, samples were collected 28 days after the last of seventeen aerial applications at approximately 130 g a.i./ha. The seed was processed using commercial type equipment. The whole cottonseed and each of the fractions produced were analysed for residues of cypermethrin. The results are shown in Table 13 (Ussary 1980, 1981). Table 13 Cypermethrin Residues in Cottonseed Process Fractions, U.S., 1979 and 1980 Process Fractions Cypermethrin Residues (mg/kg)1 I II III Whole Cottonseed 0.017 0.031 0.035 Hulls 0.019 0.038 0.021 Solvent Extracted Meal 0.008 0.006 Trace(<0.01) Crude Oil 0.15 0.20 0.16 Refined Oil 0.18 0.28 0.11 Refined, Bleached, Deodorized Oil 0.16 0.13 0.061 Deodorized Distillates 0.025 0.033 Trace (<0.01) Soapstock <0.01 <0.01 ND 1 All values corrected for analytical recovery. ND = not detected, less than 0.01 mg/kg. A sunflower seed oil processing study was conducted in Australia. Samples of air-dried seeds were extracted with hexane. The oil was refined and deodorized prior to analysis. Analysis of seed, oil and cake for cypermethrin yielded results as shown in Table 14 (Sobolewski 1981). Residues in refined, deodorized oils are approximately twice the levels found in the whole seed. In Poultry and Poultry Products Data on the nature and level of residues in meat and milk, following oral administration of cypermethrin to cows, were reviewed at the 1981 Meeting. Corresponding data are now available for eggs and poultry meat. Radiolabelled studies In a radiolabelled study, 14C-phenoxy-labelled 55:45 cis-trans cypermethrin was administered orally to laying hens daily for 14 days, at a rate equivalent to 10 ppm in the diet. Levels of radioactivity in the eggs reached a plateau on the eighth day of 0.05 mg cypermethrin equivalents/kg, predominantly in the yolk. Of the total residue in the yolk, approximately 30% was identified as cypermethrin (of unchanged cis:trans isomer ratio) and a further 4% was tentatively identified as trans-hydroxy-cypermethrin (I) (Figure 1). The remainder of the radioactivity could not be separated from the natural egg yolk lipids. Table 14 Cypermethrin Residues in Sunflower Seed Processing Fractions, Australia, 1979-80 Applications Cypermethrin Residues (mg/kg) Dose Rate Spray Rate Preharvest (g/ha) (l/ha) Interval Interval Whole Seeds Oil Cake No. (days) (days) 75 315 2 16 14 0.04 <0.01 84 21 0.03 0.04 <0.01 100 315 2 16 14 0.05 0.08 <0.01 84 21 0.04 0.09 <0.01 200 315 2 16 14 0.11 0.28 <0.01 84 21 0.08 0.17 <0.01 To examine residues in body tissues, the hens were sacrificed 4.5 hours after receiving the final dose, when levels of radioactivity in tissues were as shown in Table 15. Of the tissues analysed, the liver contained the highest levels of radioactivity (equivalent to a mean of 0.37 mg cypermethrin/kg). Of this, 0.06 mg/kg could be accounted for as cypermethrin and 0.01 mg/kg as 3-phenoxybenzoic acid. Several polar hepatic metabolites were present at levels equal to or less than that of cypermethrin itself and could not be converted in measurable quantities to either 3-phenoxybenzoic acid (IV) (3-PBA) or 4'-hydroxy- 3-phenoxybenzoic acid (V) (Figure 1). In body fat, total residues were between 0.06 and 0.10 mg/kg. 56-59% of the radioactivity in peritoneal and subcutaneous fat was due to unchanged cypermethrin. Residues in breast and leg muscle, of 0.01-0.02 mg cypermethrin equivalents/kg, were too small to facilitate characterization (Shell 1982). Table 15. Residues of Radioactive Cypermethrin and/or its Metabolites in Tissues of Laying Hens Cypermethrin residues (mg/kg) in tissues from 4 birds Tissue1 1 2 3 4 Mean S.D. Fat (peritoneal) 0.11 0.07 0.09 0.06 0.08 (0.02) Fat (subcutaneous) 0.10 0.08 0.06 0.08 0.08 (0.02) Liver 0.41 0.34 0.41 0.32 0.37 (0.05) Muscle (breast) 0.014 0.009 0.014 0.011 0.012 (0.002) Muscle (leg) 0.024 0.016 0.025 0.015 0.022 (0.005) 1 Residues measured 4 hours after the last of 14 daily oral doses of (14C-phenoxy-labelled) cypermethrin. Tissues of all birds measured in triplicate, liver in quadruplicate. These studies indicate that degradation of cypermethrin in hens initially occurs primarily by hydrolysis of the ester link, leading also to the formation of 3-(2,2-dichlorovinyl)-2, 2-dimethylcyclo- propane carboxylic acid. Hence, in the unlabelled studies described below, samples were analysed for this acid as well as for cypermethrin and 3-PBA.
Non-labelled studies In a study with 55:45 cis:trans cypermethrin, groups of 25 laying hens were fed diets containing 0.4, 4 and 40 ppm for 28 days and then returned to a control diet for an additional 14 days. Samples of eggs laid throughout the study were taken for residue analysis. Groups of five hens were sacrificed after 21, 28, 35 and 42 days to provide tissues for residue analysis. Cypermethrin levels in the whole eggs reached a plateau after approximately seven days of 0.05-0.09 mg/kg at the 40 ppm dietary level. As predicted from the radiolabelled work, these residues were present primarily in the yolk. On cessation of dosing, the levels declined rapidly to below the limit of determination of 0.01 mg/kg. Only very small levels of cypermethrin, up to 0.03 mg/kg, were detected at the lower dietary rates. Residues of cis- and trans-3- (2,2-dichlorovinyl)-2,2-dimethylcyclopropanecarboxylic acid (DCVA) (II and III) and of 3-PBA (IV) were at or below the limit of determination (0.01 mg/kg for whole eggs or 0.02 mg/kg for separated yolks and albumin) (Table 16). In the flesh, small residues of cypermethrin (up to 0.06 mg/kg) occurred following the administration of a diet containing cypermethrin at 40 ppm. These declined steadily to 0.02 mg/kg when hens were returned to a normal diet. Small residues at the limit of determination occurred at the lower dietary levels. Residue levels of DCVA and 3-PBA did not exceed the limits of determination (0.02 mg/kg and 0.01 mg/kg respectively) during the treatment period. Two weeks after administration ceased no residues of DCVA or 3-PBA could be found (Table 15). Only very small residues of cypermethrin (up to 0.03 mg/kg) were found in the liver of hens at the 4 and 40 ppm dietary rates. These declined to the limit of determination (0.01 mg/kg) or less when the hens were returned to an untreated diet. 3-PBA was just detected (0.01 mg/kg) but only at the highest dietary rate, whereas DCVA was present at up to 0.24 mg/kg at this rate and at about one tenth of this level, 0.03 mg/kg, at the 4 ppm dietary rate. (These figures refer to the 28-day feeding period.) This pattern of metabolite residues is consistent with the radiolabelled work described above. Residues of both metabolites fell rapidly to, or below, the limit of determination (0.01 mg/kg) when the hens were returned to control diet (Table 17) (Wallace and Roberts 1982). APPRAISAL Further extensive residues data on a number of crops are now available. Those on soybeans arising from a request from the 1981 Joint Meeting confirmed the MRL of 0.05 mg/kg recommended by the 1979 Meeting. Table 16 Residues of Cypermethrin and its Acid Metabolites in Whole Eggs1 Dose Compound Interval from Start of Feeding (days) Rate Measured -3 -1 3 7 14 21 25 28 31 39 42 40 CPMT NA <0.01 0.03Y 0.05 0.18Y 0.04 0.03 0.09Y 0.03 <0.01 <0.01 <0.01W <0.01W <0.01W 4.0 " NA <0.01 <0.01Y <0.01 <0.01Y 0.01 <0.01 <0.01 0.01 <0.01 <0.01 <0.01W <0.01W 0.4 " NA NA <0.01Y <0.01 <0.01Y 0.01 0.02 0.03 0.02 <0.01 <0.01 <0.01W <0.01W Control " NA NA <0.01Y <0.01 <0.01Y 0.01 <0.01 0.01 0.01 <0.01 <0.01 <0.01W <0.01W 40 DCVA <0.01 NA <0.02Y 0.01 <0.02Y 0.01 0.01 <0.02Y 0.01 <0.01 <0.01 <0.02W <0.02W <0.02W 4.0 " NA NA NA NA NA NA NA <0.01 NA NA NA 0.4 " NA NA NA NA NA NA NA NA NA NA NA Control " NA NA <0.02Y NA NA NA NA NA NA NA NA <0.02W 40 3-PBA 0.01 <0.01 <0.02Y 0.01 <0.02Y 0.01 0.01 <0.02Y 0.01 0.01 0.01 <0.02W <0.02W <0.02W 4.0 " NA NA NA NA NA NA NA 0.01 NA NA NA 0.4 " NA NA NA NA NA NA NA NA NA NA NA Control " NA NA <0.02Y NA NA NA NA NA NA NA NA <0.02W 1 Values in mg/kg unless stated otherwise; NA = not analysed; Y, egg yolk only; W,egg white only. Table 17 Residues of Cypermethrin and its Acid Metabolites in Liver and Flesh Liver (mg/kg) Flesh (mg/kg) Dose Compound Interval from start of Interval from start of feeding Rate Measured feeding (days) (days) 21 28 35 42 21 28 35 42 40 CMPT 0.03 0.021 <0.01 <0.01 0.062 0.041 0.03 0.02 4.0 " 0.01 0.03 <0.01 <0.01 0.012 0.01 0.012 <0.01 0.4 " 0.01 0.01 <0.01 0.01 0.022 0.012 0.012 0.012 Control " <0.01 <0.01 <0.01 0.01 <0.01 NA 0.012 NA 40 DCVA 0.21 0.241 0.03 0.01 <0.02 0.011 <0.02 <0.02 4.0 " 0.02 0.03 <0.01 0.01 <0.02 <0.02 <0.02 NA 0.4 " <0.01 NA3 NA NA <0.02 NA <0.02 NA Control " <0.01 <0.01 NA <0.01 <0.02 NA <0.02 <0.02 40 3-PBA 0.01 <0.011 <0.01 <0.01 0.01 <0.011 0.01 <0.01 4.0 " <0.01 <0.01 <0.01 <0.01 0.02 <0.01 <0.01 NA 0.4 " <0.01 NA NA NA 0.02 NA 0.01 NA Control " <0.01 <0.01 NA <0.01 0.02 NA 0.01 <0.01 1 Geometric mean of individual hen data; 2 Residues confirmed by GC/MS with single ion monitoring; 3 NA, not analysed. Residues data from several supervised trials on barley, carrots, kidney beans (with pod), currants, gooseberries, leeks, onions, peanuts, parsnips, swedes, spinach, sunflower seed, linseed and mushrooms enabled the Meeting to estimate maximum residue levels for these crops. The Meeting proposed that, since MRLs had now been recommended for all the major root and tuber vegetables at a level of 0.05 mg/kg, this figure could be extrapolated to the remaining members of this commodity group and a group MRL of 0.05 mg/kg was recommended. Similarly a group MRL for oilseeds, based on data on cottonseed, rapeseed, sunflower seed and linseed, was recommended at 0.2 mg/kg. Both radio-labelled and non-labelled studies on the nature and level of residues in eggs and poultry meat were reviewed. Cypermethrin levels in whole eggs reached a plateau level, after approximately seven days, of 0.05 to 0.09 mg/kg at the 40 ppm dietary level (the highest tested), the residues being mainly in the yolk. Levels declined rapidly when dosing was stopped. The highest poultry flesh levels recorded were 0.06 mg/kg during feeding a dose level of 40 ppm in the diet. In practice, it is unlikely that residues of parent compound or metabolites will reach significant levels in eggs or poultry meat, since dietary levels will seldom exceed 1 ppm in the poultry whole diet for any appreciable period. The Meeting proposed an MRL of 0.05 mg/kg for eggs and poultry meat. Further data on the effects of various methods of processing on cypermethrin residues confirmed the conclusions of the 1979 Meeting. Cypermethrin residues, being fat soluble, partition with fatty/oily fractions and usually remain unchanged, even on cooking. The Meeting estimated that the edible oil produced from vegetable oilseeds, as a group, was not likely to contain more than 0.5 mg/kg of cypermethrin. RECOMMENDATIONS The Meeting concluded that the residue levels listed below are suitable for establishing maximum residue limits. Attention is drawn to two group MRLs, which replace the individual commodities in the respective groups. MRL (mg/kg) Barley 0.5 Currants (black, red and white) 0.5 Gooseberries 0.5 Kidney beans (in pod) 0.5 Leeks 0.5 Mushrooms 0.05 Oilseeds 0.2 Onions 0.1 Peanuts 0.02 Root and tuber vegetables 0.05 (prev. potatoes and sugarbeet) Spinach 2 Eggs 0.05 Poultry meat 0.05 Edible vegetable oils 0.5 REFERENCES Robertson, S. Cypermethrin residues in sunflower seed from 1980 Argentina, ICI Plant Protection Division Residues Data, Nos. ADJ1136-7. (Unpublished) Shell Residues in eggs and tissues of domestic fowls following 1982 repeated oral dosing with (14C-phenoxy) cypermethrin. Tox. Laboratory Report SBER.82.002. (Unpublished) Shell Chimie S.A. Report No. BESR.78.052. (Unpublished) 1978 1979 Reports Nos. BEGR.79.101 and 105. (Unpublished) 1980 Reports Nos. BEGR. 030.041.045.80, 138, 144, 168, 174, 193, 194.(Unpublished) 1981 Reports Nos. BEGR.81.028,031,039,149,151,157,161. (Unpublished) 1982 Reports Nos. BEGR.82.062,085. Shell Research Ltd. Reports Nos. BLGR.80.068,072,122. (Unpublished) 1980 1981 Reports Nos. BLGR.81.027,037,108. (Unpublished) Sobolewski. Cypermethrin residues in sunflower seed, oil and cake 1981 from Australia. ICI Australia Residues Data. (Unpublished) Swaine, H., Sapiets, A., Robertson, S. and Bailey, M. Cypermethrin 1980a residues in carrot, parsnip, potato, sugar and swede. UK, 1980. ICI Plant Protection Division Residue Data Report. (Unpublished) 1980b Cypermethrin residues in black currants, gooseberry, raspberry and strawberry. UK, 1980. ICI Plant Protection Division Residue Data Report. (Unpublished) 1980c Cypermethrin residues in winter barley and winter wheat; UK, 1979-1980. ICI Plant Protection Division Residue Data Report. (Unpublished) Swaine, H., Sapiets, A., Burke, S. and Hulm, Y. Cypermethrin 1980a residues in onions: Canada, 1979. ICI Plant Protection Division Residue Data Report. (Unpublished) Swaine, H., Sapiets, A. and Farelly, E. Cypermethrin residues in 1981a onions: Canada, 1980. ICI Plant Protection Division Residue Data Report. (Unpublished) 1981b Cypermethrin residues in beans (broad, dwarf, field): UK, 1981. ICI Plant Protection Division Residue Data Report No. PP383B101. (Unpublished) 1981c Cypermethrin residues in spinach and kale: UK, 1980. ICI Plant Protection Division Residue Data Report. (Unpublished) Swaine, H., Sapiets, A, and Robertson, S. Cypermethrin black currant 1981d processing study: UK, 1981. ICI Plant Protection Division Residue Data Report No, PP383B092. (Unpublished) Swaine, H., Sapiets, A. and Farelly, E. Cypermethrin residues in 1982a Leeks: Holland, 1981. ICI Plant Protection Division Residue Data Report No. PP383 B111. (Unpublished) 1982b Cypermethrin residues in mushrooms: Holland, 1981. ICI Plant Protection Division Residue Data Report No. PP383B116. (Unpublished) Swaine, H., Sapiets, A. and Robertson, S. Cypermethrin: cabbage processing 1982c study: UK, 1981. ICI Plant Protection Division Residue Data Report No. PP383B131. (Unpublished) 1982d Cypermethrin residues in wheat and barley: Sweden, 1981. ICI Plant Protection Division Residue Data Report No. PP383B112. (Unpublished) Ussary, J.P. Cypermethrin residues in cottonseed process fractions, 1980 ICI Americas Inc., Agricultural Chemicals Division Report No. TMU0518/B (Revised). (Unpublished) Ussary, J.P. Cypermethrin residues in cottonseed process fractions. 1981 ICI Americas Inc., Agricultural Chemical Division Report No. TMU0667. (Unpublished) Ussary, J.P. Cypermethrin residues on soybeans. ICI Americas Inc. 1982 Agricultural Chemicals Division Report No. TMU0898/B. (Unpublished) Wallace, B.G. and Roberts, T.R. Cypermethrin - a residue transfer 1982 study with laying hens. Shell Research Ltd., London, Report No. SBGR. 81.283. (Unpublished)
See Also: Toxicological Abbreviations Cypermethrin (EHC 82, 1989) Cypermethrin (HSG 22, 1989) Cypermethrin (ICSC) CYPERMETHRIN (JECFA Evaluation) Cypermethrin (PIM 163) Cypermethrin (Pesticide residues in food: 1981 evaluations) Cypermethrin (Pesticide residues in food: 1983 evaluations) Cypermethrin (Pesticide residues in food: 1984 evaluations)