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 ALDICARB CH3 O H ' " / CH3SCCH = NOCN ' \ CH3 CH3 Explanation Aldicarb was reviewed by the JMPR in 1979 (FAO/WHO 1980)1/. An ADI of 0-0.001 mg/kg body weight was established, based on the no-effect level of 0.125 mg/kg bw observed in a short-term feeding study on rats. Further desirable information was noted at that time. Additional data on aldicarb metabolites have become available, primarily on aldicarb sulphone, which is one of the two major terminal residues. The other major metabolite is aldicarb sulphoxide. The data consist of acute, subchronic and chronic studies, with additional information and observations in humans, as well as a water inclusion study in rats. The data considered in support of the ADI established by the 1970 JMPR are re-evaluated in this monograph addendum in light of the additional data received, and a rationale is provided for revising the previously recommended ADI. EVALUATION FOR ACCEPTABLE DAILY INTAKE TOXICOLOGICAL STUDIES Special Study on Reproduction Rat - aldicarb sulphone Aldicarb sulphone (99.76% pure) was administered to rats (10 males and 20 females/group) at dosage levels of 0, 0.6, 2.4 and 9.6 mg/kg/day in their diet for approximately 100 days. Rats were then mated to initiate a three generation, one litter per generation, reproduction study. Fertility, gestation survival (4, 14 and 21 days) and lactation indices were determined, as well as body weights and food consumption. Male rats fed 9.6 mg/kg exhibited reduced body weights. There were no differences from the control with regard to fertility, gestation survival or viability indices. Marginal effects 1/ See Annex 2 for WHO and FAO documentation. on the lactation index were noted. It was determined that aldicarb sulphone, at levels up to and including 9.6 mg/kg, was without adverse effects on reproduction under the conditions of this study (Woodside et al 1977a). Special Study on Teratogenicity Rat - aldicarb sulphone The aldicarb sulphone reproduction study conducted by Woodside et al (1977a) incorporated a teratology bioassay. The animals were divided into four groups and orally dosed with either 0, 0.6, 2.4 or 9.6 mg/kg at one of the following time intervals of gestation: 0-20 days, 6-15 days, or 7-9 days. All animals were sacrificed before parturition (day 20) and the foetuses examined for skeletal and visceral changes. Resorption sites, number and condition of pups and litter weights were recorded. The pregnancy rate was unaffected by treatment, except that resorption sites per female were slightly increased in 9.6 mg/kg-treated females for the 6-15 day treatment interval. No increase in resorption was seen at the same dosage level for days 0-20. Anomalies were essentially non-existent and there was no indication of terata produced under the conditions of the study at levels up to and including 9.6 mg/kg. Special Study for Carcinogenicity Mice - aldicarb sulphone Groups of Charles River CD-1 mice (50/sex/group) were administered 0, 0.15, 0.6, 2.4 and 9.6 mg/kg aldicarb sulphone in the feed for 18 months. Mice were housed two per cage in the first year and singly thereafter. Observations were made routinely throughout and included mortality, food consumption and body weight determinations. Gross and microscopic examination were performed on all mice. Body weight changes were sporadic and exhibited no trends. Histologic changes were not statistically different from controls at any dose level for either sex. Based on these criteria, aldicarb sulphone did not affect tumour incidence or produce any pathological alteration in this strain of mouse (Woodside et al 1977b). Special Study on Neurotoxicity Hen - aldicarb sulphone Adult white Leghorn hens (40 each) were intubated to receive 250 mg/kg bw aldicarb sulphone suspended in maize oil. Two other groups, each with 10 hens, received either TOCP (500 mg/kg) or maize oil alone, and served as positive and negative control groups respectively. The birds received single oral doses, 21 days apart, in a typical acute delayed neurotoxicity evaluation. The hens were observed every third day for 42 days. There were no neurological effects other than acute cholinergic signs of poisoning in the TOCP dosed group. No histological examination was performed, owing to the lack of demonstrated neurotoxic signs. Aldicarb sulphone did not cause delayed neurotoxic reactions under the conditions of the study (Babish and Salerno 1977). Special Study on Sensitization Skin sensitization to aldicarb sulphone (UC 21865, technical) or a 75% WP formulation was evaluated in albino guinea pigs (Hartley Strain) using a modified Landsteiner technique. Neither substance was determined to be a sensitizer under the conditions of this study (Conroy and Carpenter 1977). Acute Toxicity The acute toxicity of aldicarb, aldicarb metabolites and of aldicarb formulations to several animal species is summarized in Table 1. Aldicarb is very highly toxic to mammals by oral exposure. In all species tested, the acute oral toxicity of aldicarb and its formulations are similar. The oral toxicity of the formulations is basically that associated with ingestion of the active toxicant; the lower acute oral toxicity of aldicarb formulations reflects the reduced concentrations of aldicarb as formulated in the granular material. The toxicity of aldicarb when injected intraperitoneally or intravenously is substantially similar to the toxicity via the oral route, suggesting rapid absorption into the body. Aldicarb is also highly toxic by dermal exposure; it readily penetrates the skin, especially moist skin. In contrast, the dermal toxicity of TEMIKR formulations is extremely low, reflecting the greatly reduced availability of aldicarb from the formulations. Moistening the TemikR formulation on the skin during dermal exposure similarly enhances penetration of aldicarb; granular TemikR formulations are more toxic in contact with moist skin than with dry skin. The oral toxicities of aldicarb and its principal metabolite, aldicarb sulphoxide, are similar, while the oral toxicity of aldicarb sulphone is approximately 4% that of aldicarb. The other aldicarb metabolites are considerably less toxic than these. Table 1. Acute Toxicity of Aldicarb and Its Metabolites in Animals LD50 Chemical Species Sex Route Vehicle (mg/kg bw) Reference Aldicarb Guinea pig oral maize oil 1.0 Nycum and Carpenter 1968 Rabbit oral propylene glycol 1.3 " Rat M dermal maize oil >10 Field 1979b Rabbit M dermal maize oil >10 Field 1979a Aldicarb Metabolites Aldicarb Mouse M oral maize oil 0.8-1.6 Nycum and Carpenter 1968 sulphoxide Guinea pig oral maize oil 0.8-1.8 " Rabbit oral maize oil 0.4-1.8 " Rat M i.p. maize oil 0.71 Johnson and Carpenter 1966 Aldicarb sulphone Mouse M oral maize oil 25 Nycum and Carpenter 1968 Guinea pig oral maize oil >50 " Rabbit oral maize oil 75 " Table 1 (con't) LD50 Chemical Species Sex Route Vehicle (mg/kg bw) Reference Aldicarb Formulations 10 G gypsum Rat M oral none 7.07 Weil and Carpenter 1972 TSX (a) Rat M oral maize oil 7.9 Wolfe and Bristol 1980 Rat F oral maize oil 6.7 " 10G gypsum Rabbit F oral none 7.9-17.8 Myers et al 1975b; Weil maize cob and Carpenter 1974a 15G gypsum Rabbit F oral none 5.29-10.6 Myers et al 1975b; Weil maize cob and Carpenter 1974a 15G maize cob Rabbit F oral none 8.4 Myers et al 1975b 10G gypsum Rat M&F dermal dry 2100->5000 Myers et al 1975b; Weil and maize cob Carpenter 1970, 1971, 1972, 1974a 10G gypsum Rat M&F dermal water 283-673 Myers et al 1975a,b; Weil and maize cob Carpenter, 1968, 1969, 1974a. 15G gypsum Rat M&F dermal dry 1980-6320 Myers et al 1975b; Weil and maize cob Carpenter 1971, 1972, 1974a. Rat M&F dermal water 283-1010 Myers et al 1975b; Weil and Carpenter 1974a. Table 1 (con't) LD50 Chemical Species Sex Route Vehicle (mg/kg bw) Reference Aldicarb Formulations (con't) 10G gypsum Rabbit M dermal dry >4800 Weil and Carpenter 1974a 15G gypsum Rabbit M dermal dry >4800 " TSX1/ Rabbit M&F dermal none >2000 Wolfe et al 1980 1/ TSX is a mixture of Temik (5.5%), Terrachlor fungicide (9.5%) and Terrazole fungicide (2.3%). Short-Term Studies Mice - aldicarb sulphone Groups of Charles River, CD-1 mice (5/sex/group) were fed aldicarb sulphone in the diet at levels of 0, 0.15, 0.6, 2.4, 9.6 and 38.4 mg/kg for seven days. Body weights were determined on three separate days. Mice were observed daily for signs of toxicity or abnormality. Selected organ weights (liver and kidneys) were measured and their absolute and relative organ weights determined. It was concluded that only the highest dose produced statistically significant body weight decrease. There were no dose-related or statistically significant organ weight changes. Cholinesterase values were not determined (Weil and Carpenter 1974b). Rat - aldicarb Groups of CFE rats (10 per sex per group) were fed aldicarb in their diet for 93 days at dosage levels of 0, 0.02, 0.1 and 0.5 mg/kg body weight. One rat per level was killed for cholinesterase (plasma, RBC and brain) determinations at 1 or 2, 4 and 29 days of dosing. Body weights, diet consumption and selected organ weights (liver and kidney) were determined, and histopathological examination of lung, liver, kidney and trachea were done. Mortality was increased for the highest dose levels, statistically at the 0.5 mg/kg bw dose level. Body weight and food consumption were also decreased at the highest level. Relative liver and kidney weights were not affected at any dose level in comparison to control. Histopathology of the selected organs was unremarkable and there were no compound-related effects noted. There were no consistent dose-related effects on the cholinesterase determinations, except for plasma cholinesterase depression in both sexes after 30 days at the highest level. There was no indication of how soon after feeding the ChE determinations were performed, which could account for the sporadic results, together with the small number of animals sampled at each interval (Weil and Carpenter 1963). Rat - aldicarb sulphoxide: aldicarb sulphone (1:1) Wistar rats (10 males and 10 females per group) were administered aldicarb sulphoxide and aldicarb sulphone in a 1:1 ratio, in the drinking water, ad libitum, for 29 days. Nominal dose levels were 0, 0.075, 0.3, 1.2, 4.8 and 19.2 ppm. Body weight, food and water consumption, and clinical haematology parameters were measured weekly. Plasma and red blood cell cholinesterase levels were determined after 8, 15 and 29 days of treatment. Brain cholinesterase was measured at termination. Animals were continuously exposed to the test substances in water until blood samples were taken or sacrifice was performed, Cholinesterase activity in blood and brain was analysed by a modification of an automated procedure described by Humiston and Wright (1965), which is an adaptation of the method described by Ellman et al (1961). Preliminary in vitro enzyme inhibition kinetic studies verify the methodology as acceptable for defining reversible carbamate-induced cholinesterase inhibition in rats. Significant depression of plasma, RBC and brain cholinesterase, in both sexes, occurred at the highest dose level. Sporadic differences in plasma and RBC cholinesterase values, which occurred in males only, were inconsistently depressed and within the range of biological variability. The data demonstrate that a level of 4.8 ppm of aldicarb sulphoxide: aldicarb sulphone in water is without effect on cholinesterase (plasma, RBC, brain) in either sex. Based on the actual concentrations being approximately 80% of the nominal values, the no- effect level is roughly 3.84 ppm or 0.384 mg/kg (in water). Food and water consumption values together with body weight gains were significantly decreased in both sexes at the high dose level when compared to controls. There were no such differences at any of the other dose levels. There was no mortality (Mirro et al 1982). Rabbit - aldicarb sulphone (dermal) Aldicarb sulphone (technical and 75 WP) were administered to the unabraded, but closely clipped, ventral surface of rabbits (6 males/group, 5 days/week for 19 applications) at dosages of 4.8 mg/kg bw for 75 WP and 3.5, 7.0 and 14.0 mg/kg bw for technical aldicarb sulphone. No mortality, skin irritation or cholinesterase depression were observed. However, rabbits were removed from treatment 19 hours prior to ChE analysis, which could account for the lack of response (ChE depression) considering the rapid reversibility of ChE inhibition for aldicarb and its ChE-inhibiting metabolites. Body weight was significantly depressed in the high dose level rabbits. There were no reported treatment-related effects on organ weights or organ-to-body weight ratios (liver, kidney, brain). Necropsy findings were unremarkable (Weil et al 1977). Observations in Humans Fifteen male volunteers participated in a study in Panama to evaluate human exposure in a banana plantation where Temik-15G was applied under natural conditions. Temperatures ranged from 75°F (24°C) to 92°F (32°C) with 80 to 90% relative humidity. The workers used three different types of hand-held applicators. Blood samples were taken from all volunteers prior to initiating the test and immediately following each 6-hour working period. Samples were obtained in the field and analysed 1-2 hours later in the laboratory using the Boehringer Mannheim method, a photometric test based on the method of Ellman et al (1961). Urine samples were also collected. Only two workers showed greater than 25% reduction in their blood cholinesterase activity (29% and 50%). Spontaneous reversibility was evident in both cases. The worker with 50% reduction showed 25% recovery within three hours. Blood samples from the other worker indicated 100% recovery 24 hours later. Results of blood analyses indicated that cholinesterase activity was below the normal range (population) in samples collected from six workers during the second day of the study. Cholinesterase activity in all samples taken during the first and third day of the study were within the normal range. No clinical signs of aldicarb-induced intoxication were found, although one individual presented symptoms of nausea, stomachache and headache (Union Carbide 1979). COMMENTS Aldicarb, the active ingredient of the nematocide-insecticide sold under the trade name TEMIKR, is rapidly absorbed and metabolized by mammals to aldicarb sulphoxide, its major metabolite. Aldicarb sulphoxide is more slowly degraded to aldicarb sulphone. All metabolites of aldicarb, both oxidative and hydrolytic, are rapidly and completely eliminated from the body, 80-90% being excreted within 24 hours, and leave no detectable residues by the fifth day. Data demonstrate that they are not stored in body tissues. The toxicological properties of aldicarb and its metabolites have been assessed in several species of laboratory animals under a variety of exposure conditions (acute, subchronic and chronic) and routes (oral by gavage, diet and drinking water; dermal; inhalation and injection). Aldicarb is extremely toxic acutely, with an oral LD50 in rats of approximately 1 mg/kg body weight. Aldicarb sulphoxide is a more potent acetylcholinesterase inhibitor than aldicarb, and the rapid conversion in animals to aldicarb sulphoxide is probably responsible for the acute toxic reaction associated with aldicarb. The acute toxicity of aldicarb sulphone is considerably less (LD50 = 20-25 mg/kg) than either aldicarb or aldicarb sulphoxide. Studies examining the acute and subchronic effects of aldicarb administered orally to human volunteers and under a variety of actual working conditions reveal the same pattern of acetylcholinesterase depression and rapid recovery as that demonstrated in experimental animals. Depressed cholinesterase levels return rapidly to normal and symptoms, if any, subside immediately following removal from exposure to aldicarb. There have been no lasting effects on the health of volunteers exposed to aldicarb under natural or laboratory conditions. The toxicological responses of humans to aldicarb and its metabolites, under such conditions, do not differ from those of laboratory animals. Aldicarb's inhibitory effect on acetylcholinesterase is rapidly reversed following hydrolysis of the carbamylated enzyme to regenerate active enzyme. In experimental animals and humans, spontaneous recovery from sublethal doses of aldicarb occurs very rapidly (within a few hours of exposure). The competition of acetylcholine and aldicarb for the enzyme's active site, the instability of carbamylated enzyme, together with the efficient metabolism and high aqueous solubility of aldicarb, contribute to the spontaneous rapid recovery of inhibited enzyme. The rate at which acetylcholinesterase activity recovers makes it difficult to measure acetylcholinesterase inhibition analytically in the laboratory, and rapid assays must be used under carefully controls conditions. Short-term and long-term studies with aldicarb and its sulphone and sulphoxide metabolites have revealed no neurological, carcinogenic, mutagenic or teratogenic effects, and no adverse effect on reproduction. At a dietary dose of 0.25 mg/kg/day, a minimal depression of blood cholinesterase was observed in rats. In dogs, a no-effect level was noted at 0.25 mg/kg/day. Cholinesterase levels (RBC and plasma) were apparently unaffected in this study, although these were measured after a period that allowed the spontaneous recovery of the enzyme. In a subchronic study where aldicarb sulphoxide and sulphone were added to drinking water in a 1:1 ratio, the no-effect level was observed to be 4.8 ppm, based on cholinesterase depression. In a 6-month rat feeding study with the sulphoxide metabolite, the no-effect level for cholinesterase depression has been accepted as 0.125 mg/kg body weight, with no other effects observed at higher doses. These studies demonstrate that the method of administering the dose to the animal can greatly modify the toxic properties of aldicarb, as contrasted in the acute oral versus short- and long-term dietary studies. Rats, mice and dogs have tolerated LD50 doses repeatedly administered from 7 days to 2 years, when incorporated in their diet. Similarly, a 1:1 mixture of aldicarb sulphoxide and aldicarb sulphone when administered in the drinking water to rats for 28 consecutive days at doses equivalent to the LD50 for aldicarb sulphoxide (e.g. 0.38 to 1.5 mg/kg bw) caused no deaths and only moderate ChE depression at the high dose. Conversely, a single bolus of aldicarb or aldicarb sulphoxide equivalent to the above doses, when administered by gavage or intubation to laboratory animals, caused death in less than 2 hours. This ability of all animals to survive daily doses of aldicarb equivalent to single-dose LD50 values suggests the reduced bioavailability of aldicarb when administered in the diet. Human volunteers tolerated single oral doses of aqueous solutions of aldicarb (in doses of 0.025, 0.05 or 0.1 mg/kg) with only mild depression of whole blood cholinesterase in all cases. Only the persons receiving 0.1 mg/kg aldicarb presented symptoms of acute cholinergic stress (i.e. nausea, sweating, pin-point pupils, salivation). These data indicate that humans are no more sensitive to aldicarb, aldicarb sulphoxide or aldicarb sulphone than laboratory animals. In the light of the data on aldicarb, the spontaneous recovery of the carbamylated cholinesterase enzyme within a few hours and the reduced bioavailability from dietary exposure, it is unlikely that humans exposed to residues of aldicarb in food will suffer any prolonged or significant cholinesterase depression, provided such residues are from purposeful use in accordance with GAP (good agricultural practice) and within established international limits (MRLs). This is suggested by the no-effect levels determined from reproduction, teratogenic, carcinogenic, neurotoxic, subchronic and chronic dietary studies. ChE inhibition is transient and recovery is rapid and spontaneous. Accordingly, the Committee has revised the ADI to reflect more accurately the concern for aldicarb residues that may be present in foodstuffs. TOXICOLOGICAL EVALUATION Level Causing no Toxicological Effects Rat: 2.5 ppm in the diet, equivalent to 0.125 mg/kg bw. Dog: 0.25 mg/kg bw Estimate of Acceptable Daily Intake for Man 0 - 0.005 mg/kg bw. REFERENCES Babish, J.G. and Salerno, A. Neurotoxicity evaluation of UC 21865 1977 in white Leghorn hens (Gallus domesticus). Report from Food and Drug Research Laboratories submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Conroy, W.J. and Carpenter, C.P. UC 21865 Technical and 75% WP sensitization potential 1977 in guinea pigs as determined by intradermal injection. Report from Carnegie-Mellon Institute (No. 40-12) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Ellmann, G.L. Courtney, K.D., Andres, V. Jr. and Featherstone, R.M. 1961 A new and rapid colorimetric determination of acetylcholinesterase activity. Biochem. Pharmacol. 7:88. Field, W.E. Acute dermal toxicity in rabbits. Report from CDC 1979a Research, Inc, (CDC-UC-009-79) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) 1979b Acute dermal toxicity in rats. Report from CDC Research, Inc. (CDC-UC-008-79) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Humiston, C.G. and Wright, G.J. A new automated method for the 1965 determination of cholinesterase activity. Clin. Chem. 11:802. Johnson, H.E. and Carpenter, C.P. Temik (technical grade compound 1966 21149). Comparative behavioural effect in rats. Report from Mellon Institute (No. 29-89) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Myers, R.C., Weil, C.W. and Carpenter, C.P. Temik, 10G: Acute 4-hour 1975a skin penetration of rats. Report from Mellon Institute (no. 38-40) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Myers, R.C., Weil, C.S. and Cox, E.F. Temik 19G B.C. (coal); 10G and 1975b 15G (gypsum); 15G (corn cob). Comparative toxicity studies via peroral, dermal and inhalation routes. Report from Mellon Institute (no. 38-141) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Mirro, E.J., DePass, L.R. and Frank, F.R. Twenty-nine day water 1982 inclusion study in rats. Report from Bushy Run Research Laboratory (no. 45-181) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Nycum, J.S. and Carpenter, C.P. Toxicity studies on Temik and 1968 related carbamates. Report from Mellon Institute (no. 31-48) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Union Carbide. Volunteer worker's exposure monitoring study 1979 (Panama). Report from Union Carbide Corporation submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Weil, C.S. and Carpenter, C.P. Results of three months of inclusion 1963 of Compound 21149 in the diet of rats. Report from Mellon Institute (No. 26-47) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) 1968 Temik 10G-V (10.3% granular formulation of Compound 21149). Acute and 14-day dermal application to rabbits. Report from Mellon Institute (no. 31-137) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) 1969 Four-hour wet skin contact test on rats. Report from Mellon Institute (no. 32-64) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Weil, C.S. and Carpenter, C.P. Comparative skin penetration toxicity 1970 of Temik 10GV and 15 other pesticide formulations as marketed. Report from Mellon Institute (No. 33-15) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) 1971 Comparative skin penetration toxicity of Temik, Temik 10GV, Temik 15GV, and 5 other pesticide formulations as marketed. Report from Mellon Institute (No. 34-76) submitted to the World Health Organization. (Unpublished) 1972 Miscellaneous toxicity studies. Report from Mellon Institute (No. 35-41) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) 1974a Temik aldicarb pesticide 10G and 15G. Range-finding toxicity studies. Report from Mellon Institute (no. 37-39) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) 1974b UC 21865; results of feeding in the diet of mice for 7 days. Report from Mellon Institute (No. 37-89) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Weil, C.S., Conroy, W.J., Condra, N.I. and Cox, E.F. Aldicarb 1977 sulphone UC 21865. 19-day rabbit skin inunction. Report from Mellon Institute (No. 40-13) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Woodside, M.D., Weil, C.S. and Cox, E.F. Inclusion in the diet of 1977a rats for three generations (aldicarb sulphone), dominant lethal mutagenesis and teratology studies. Report from Carnegie Mellon (no. 40-1) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) 1977b Aldicarb sulphone; 18-month feeding in the diet of mice. Report from Carnegie Mellon (No. 40-38) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Wolfe, G.W. and Bristol, K.L. Acute oral toxicity study in rats. Temik 1980 TSX. Report from Hazleton Laboratories America, Inc. (Report 400-631) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) Wolfe, G.W., Voelker, R.W. and Dauvin, E.M. Acute dermal toxicity 1980 studies in rabbits. Temik TSX. Report from Hazleton Laboratories America, Inc., (Report 400-632) submitted to the World Health Organization by Union Carbide Corporation. (Unpublished) ALDICARB CH3 O H ' " / CH3SCCH = NOCN ' \ CH3 CH3 Explanation Aldicarb was reviewed by the Joint Meeting in 1979 (FAO/WHO 1980b)1/ and maximum residue levels estimated for several major commodities. As a result of actions and discussions by the Thirteenth and Fourteenth Sessions of the Codex Committee on Pesticide Residues (CCPR), additional residue data and good agricultural practice (GAP) information or other information have been provided to the Meeting for citrus, potatoes and milk. Residue data and GAP information have also been provided for the first time for several additional commodities. These new submissions are reviewed in this addendum. RESIDUES IN FOOD AND THEIR EVALUATION USE PATTERN Aldicarb is sold as a granular formulation (0.5-15% active ingredient). It may be applied at the stage of pre-planting, planting, post-emergence or in some crops before or as the new growth begins. Application may be broadcast or band and the granules are typically covered with or worked into the soil. A more extensive description has been provided previously (FAO/WHO 1980b). Labels for currently registered U.S. uses as well as information on proposed uses were available to this Meeting and are summarized in Table 1. Typically only one application annually is recommended. The manufacturer informed the Meeting that U.S. use directions will cover most user situations. The manufacturer provided limited agricultural practice information for Argentina, Brazil, France, Mexico, South Africa and the United Kingdom. This information and new information provided by the Netherlands' government are summarized in Table 2. RESIDUES RESULTING FROM SUPERVISED TRIALS Brussels sprouts Residue data were available from 1980 (CIVO 1981) and 1981 (CIVO 1982) supervised trials in the Netherlands. The data resulted from single applications at planting or one day preplanting of 10G 1/ See Annex 2 for FAO and WHO documentation. Table 1. Summary of U.S. Federally Registered and Proposes Uses for Aldicarb on Various Commodities Registered Uses1/ Time of kg a.i./ha Preharvest Commodity Formulation Application or 100 m of row Interval (days) Beans (dry) 15G at planting 0.59-2.4 90 Citrus 15G prior to or 5.5-11.3 30 (for (grapefruit, during lemons) lemons, limes, spring flush oranges) or new growth Cotton 15G at planting 0.34-3.4 90 Grain sorghum 15G at planting 0.59-1.2 902/ or 6-9.8 g/100 m Peanuts 15G at planting 1.2-3.4 90 Pecans 15G bud break to 5.5-11.3 - nut set Potatoes 15G at planting 1.2-3.5 90 or after planting 2.3-3.3 or 9.8-30 g/100 m 50 Soybeans 15G at planting 0.84-3.4 90 Sugarbeets 15G at planting 1.8-2.3 90 1 week before Sugarcane 15G at planting 2.4-3.4 120 (Louisiana only) or 36-52 g/100 m Sweet potatoes 15G at planting 1.7-3.4 120 (also or a restriction 21-43 g/100 m on vines) Table 1 (con't) Time of kg a.i./ha Preharvest Commodity Formulation Application or 100 m of row Interval (days) Grapes 10G just prior to 4.5 120 or or at 15 G beginning of active vine growth Maize 10G at planting 1.1-1.7 60-day (field corn) or forage feed 10-15 g/100 m restriction. 15G at planting 1.1-1.7 60-day or forage feed 7-10 g/100 m restriction. Tomatoes3/ 10G at or just 2.2-3.4 (field grown) prior to or transplanting 35-54 g/100 m or seeding (10g and 15g) 15G 2.2-3.4 or 39-55 g/100 m 1/ U.S. EPA Reg. No. 264-330; EPA EST. 10352-GA-01; 2/ Feeding or foraging before harvest is not recommended as residue levels on green forage may be unsafe for animals; 3/ Proposed use limited to California and Florida. Table 2. Summary of Aldicarb Uses in Several Countries1/ Crop Country Formulation Application Preharvest Rate Interval (days) Banana Brazil 10G 2-3 g a.i./cova 21 South Africa 15G 3 g a.i./station (new plt.) 2.6-3 g a.i./mat twice a year (established) Beans Brazil 10G 1-2 kg a.i./ha 80 or 5-10 kg/100 m Beet Netherlands 10G 1.2-2.5 kg a.i./ha entire growing (sugarbeet (row at plt.) period. and fodder) Brussels Netherlands 10G 3 kg a.i./ha entire growing sprouts (broadcast, period worked in) Citrus Brazil 10G 1-5 g/cova 60 10-20 g/adult tree Coffee Brazil 10G 3-15 g/cova 90 Cotton Argentina 10G 0.3-3 kg a.i./ha Brazil 10G 0.6-2 kg a.i/ha South Africa 15G 0.5-1.5 kg a.i./ha Figs Brazil 10G 5-10 kg a.i./ha Garlic Argentina 10G 0.5-3 kg a.i./ha Leaf U.K. 10G 5.1 g/100 m 70 brassicas2/ (cabbage, cauliflower, Brussels sprouts) Maize and U.K. 10G 5.1 g/100 m sweet corn2/ South Africa 15G3/ 11-15 g/100 m Table 2 (con't) Crop Country Formulation Application Preharvest Rate Interval (days) Onions Argentina 10G 0.5-3 kg a.i./ha Onions Netherlands 10G 1.5 kg a.i./ha entire growing (bulbs) (row at sowing) period Oranges Argentina 10G 22 g/plant Peanuts Argentina 10G 0.3-2 kg a.i./ha Peas2/ U.K. 10G 1 kg a.i./ha (preplant broadcast) Peppers Argentina 10G 1-3 kg a.i./ha Potatoes South Africa 15G 2.6-7.5 kg a.i./ha Netherlands 10G 3 kg a.i./ha (broadcast and work in shortly before plt.) Ratoon cane South Africa 15G 2.3-3 kg a.i./ha Sugarcane South Africa 10G 3 kg a.i./ha Brazil 10G 2-3 kg a.i./ha Argentina 10G 1.5-3 kg a.i./ha Swedes and U.K. 10G 7.7 g/100 m row turnips2/ at planting Sweet Argentina 10G 2-3 kg a.i./ha potatoes Brazil 10G 1-2 kg a.i./ha Tomatoes Argentina 10G 0.5-3 kg a.i./ha U.K. 10G 55 g active/100 m2 (in propagating house) 0.1 a.i./plant (spot) 75 g a.i./100 m2 1/ Information for Mexico and France was too limited to be useful; 2/ Cleared until 31 March 1981 U.K.; 3/ Only maize. formulation at or at twice the approved rate (Table 2). At the approved application rate residues were 0.01 and 0.02 (0.01- 0.03 mg/kg) at 133 and 150 days, respectively, after treatment. At twice the approved rate, residues were 0.01 and 0.05 (0.04-0.07 mg/kg) at the same respective periods. In each case, the number of samples could not be determined from the submission. The values are uncorrected for approximately 85% analytical method recoveries at 0.05 and 0.06 mg/kg fortification levels. Citrus The current 0.2 mg/kg limit is based on extensive data, including over 200 samples on oranges alone, and on a 90-day preharvest interval (FAO/WHO 1980b). Additional data have been provided to this Meeting and have been examined in conjunction with data previously submitted, along with information on current good agricultural practices. These additional data include residue data for over 160 additional citrus samples, including lemons and different varieties of grapefruit and oranges. Residues in the three lemon samples were < 0.1 mg/kg a.i. at 30-90 days after treatment at the recommended 11 kg a.i./ha. Residues in grapefruit were < 0.02 for all 18 samples, although the preharvest intervals were 158-300 days for all 18 samples, except for one sample (0.02 mg/kg) at 42 days. Of the 100 orange samples, only one mature fruit sample had residues at the current 0.2 mg/kg limit at > 90-day preharvest interval and a < 11 kg a.i./ha recommended application rate. However, maximum residues from this application rate were 0.29 and 0.31 mg/kg at a 30-day interval and 0.21 at 60 days. With these recent submissions, the Meeting has examined data for well over 600 samples of various types and varieties of citrus, representing mature whole fruit, immature fruit, peel, pulp, numerous locations, application rates (recommended and higher), types of applications, cooperators, pre-harvest intervals and split treatments. These data and conditions are too numerous for tabulation in a concise manner suitable to this document. Of the total of over 600 samples, about one third were treated at approximately the maximum recommended rate (excluding higher rates); these accounted for most of the samples with residues in excess of the current 0.2 mg/kg limit. Those samples on mature or ripe citrus, and a few where the stage of maturity is unknown, with residues exceeding 0.2 mg/kg are summarized in Table 3. It can be observed that most residues exceeding 0.2 mg/kg are at intervals after application of less than the 90-day basis for the current limit. Some of these resulted from other than recommended agricultural practices. However, it was brought to the attention of the Meeting that some varieties of citrus have overlapping spring flush and harvesting seasons (e.g. Valencia) or have continuous fruit harvesting (lemons). For this reason, preharvest intervals on the order of 30 to 60 days can be pertinent in practice in some Table 3. Citrus Samples with Aldicarb Residue Exceeding the Current 0.2 mg/kg Limit1/ Interval After Species Date Type of Aldicarb Rate Last Treatment Part Residues Location (Variety) Treated Treatment (lb a.i./A)* (days) Sampled (mg/kg) Florida Orange 7-30-74 Two 76 cm 10 31 full size fruit, (Valencia) strips, one pulp 0.11 0.22 on each peel 0.54 (whole basis) side of tree Florida Orange 7-30-74 Two 76 cm 10 199 Mature ripe 0.23 (Valencia) strips, one fruit on each side of tree 10 15 Ripe fruit 0.213/ 30 Ripe fruit 0.253/ 60 Ripe fruit 0.363/ Arizona Orange (Valencia) 3-31-75 Applied with 10 45 Whole mature 0.432/ cyclone spreader, ripe fruit disc incorporated, 60 Whole mature 0.292/ then irrigated2/ ripe fruit Arizona Orange (Valencia) 3-31-75 Split application2/ 5+5 0 Mature ripe 0.282/ and fruit 5-30-75 Applied as above Table 3 (con't) Interval After Species Date Type of Aldicarb Rate Last Treatment Part Residues Location (Variety) Treated Treatment (lb a.i./A)* (days) Sampled (mg/kg) Florida Orange 3-25-76 Banded and 10 60 Ripe fruit 0.214/ (Valencia) incorporated on two sides of tree row Florida Orange 3-25-76 Injected into a 10 30 Ripe fruit 0.214/ (Valencia) band on two sides of tree 60 Ripe fruit 0.294/ Arizona Orange 2-15-77 1.2 m band along 10 60 Ripe fruit 0.25 (Valencia) two sides of tree row Israel Orange 5-31-76 Applied beneath 7 47 "whole fruit" 0.23 (Valencia) tree dripline and incorporated 7 47 "whole fruit" 0.34 Florida Grapefruit 4-8-77 Broadcast and 10 61 Mature fruit 0.22 (variety incorporated in not given) a band under trees Florida Grapefruit 4-8-77 Incorporated 10 42 Mature fruit 0.21 (Marsh) under trees Table 3 (con't) Interval After Species Date Type of Aldicarb Rate Last Treatment Part Residues Location (Variety) Treated Treatment (lb a.i./A)* (days) Sampled (mg/kg) Peru Lime 7-23-80 Hand 4.5 31 Mature fruit 0.235/ application 6.25 31 Mature fruit 0.265/ Mexico Lime 4-7-81 Hand application 7.9 42 "whole fruit" 0.345/ (Cridlo) incorporated by 10.7 42 "whole fruit" 0.445/ irrigation on 4-9-81 * 1 lb/A = 1.1 kg/ha 1/ Citrus data sheets previously submitted and newly submitted are in Supplementary Book III of IV, Aldicarb Residue Data on Citrus, July 1982, submitted by Union Carbide Agricultural Products, Inc. P.O. Box 12014, T.W. Alexander Drive, Research Triangle Park, North Carolina 277091. Those data previously submitted and the basis for the current 0.2 mg/kg limit were also submitted to the U.S. Environmental Protection Agency in tolerance petitions GF1829 and 9F2201. 2/ Not applied in manner consistent with use directions. 3/ Previously treated 8 months (244 days) earlier which is not consistent with use directions of approximately one year. 4/ "New Residue Data on Citrus", see Ref. 1 for source. 5/ Original studies unavailable. situations, especially for lemons and Valencia. Although none of the 18 samples of lemons contained residues above 0.1 mg/kg, only two were harvested at intervals of approximately the 30-day interval that is considered good agricultural practice (Table 1). All but three were at 91 days or over and most over 140 days. Data on limes (Table 3) do not exceed 0.3 mg/kg at 42 days although the stage of fruit maturity is unknown. Grapes Aldicarb is not currently registered for use on bearing grapes although it is said to be registered for nursery grapes in five countries. All discussions here are based on proposed uses in the U.S. (Table 1), from which residue data are available. Residue data are available from 8 states in the U.S. (Table 4), reflecting the proposed application rate of 4.5 kg a.i./ha, and include samples from 58-133 days after last application (120 days recommended). The type of treatment varies widely among the samples. In many, if not most, the types of treatment either do not closely follow that of the proposed use or insufficient information is available to determine just how close the proposed good agricultural practices are followed. Most of the higher residues resulted from treatments with intervals of last treatment to harvest substantially less than the 120 days recommended. At intervals approximately at or exceeding the 120 days, maximum residues are <0.3 mg/kg except for one value at 0.49 mg/kg (sample 7). Two other samples from the same cooperator at the same and different times (samples 8 and 9) were much lower, although the methods of application were different. Residue data were available from processing of grapes (Table 5) and includes data on raisins, fresh juice, pomace and dry pomace, wine, stems, trash and leaves (see also Fate of Residues - In Storage and Processing). The limit of detection for aldicarb in grapes is approximately 0.02 mg/kg. Recoveries averaged about 87% at fortification levels ranging from 0.04 - 0.9 mg/kg. Maize The Meeting was informed that maize is registered for use in six countries, although no residue data or current good agricultural practice information was available for those countries. Data were available from 27 trials in 13 states in the U.S. representing proposed good agricultural practice. Data for grain, cobs, green kernels and green kernels plus cob are summarized in Table 6 (Union Carbide 1982a and 1982b). From 48 samples of mature grain representing Table 4. Aldicarb Residues in Ripe Grapes Interval between Location Year Variety Rate Treatment and Residues2/ Recovery lb a.i./A1/ Harvest (days) (mg/kg) (%) PA 1977 Concord 0 <0.02 87 4 102 0.03 PA 1978 Concord 4 133 <0.02 87 OH 1977 Clinton 4 110 0.03 87 OH 1978 Clinton 0 <0.02 87 4 89 0.02 OH 1979 Clinton 0 <0.02 85 4 109 0.04 OH 1980 Clinton 0 <0.01 91 4 115 0.01 WA 1977 Concord 0 0.033/ 87 4 116 0.494/ (shanked) 4 (broadcast) 116 <0.02 WA 1980 Concord 0 <0.02 94 4 133 <0.02 (76 cm band incorp. 5 cm) Table 4. (con't) Interval between Location Year Variety Rate Treatment and Residues2/ Recovery lb a.i./A1/ Harvest (days) (mg/kg) (%) AZ 1978 Thompson 4 62 0.29 (shanked, both sides) AR 1980 Concord 0 <0.01 91 4 118 <0.03 OR 1979 Concord 0 <0.02 73 4 125 0.19 (61 cm area drip line 2 sides disced) MI 1980 Concord 0 <0.01 91 4 92 <0.01 CA 1978 Thompson 0 <0.02 87 4 122 <0.02 0 <0.02 87 4 120 <0.02 CA 1977 Thompson 0 0.02 87 4 93 0.42 (91 cm band shanked 2 sides) Table 4. (con't) Interval between Location Year Variety Rate Treatment and Residues2/ Recovery lb a.i./A1/ Harvest (days) (mg/kg) (%) CA 1978 Thompson 4 131 0.08 87 4 122 0.23 87 4 120 0.05 87 (91 cm band raked in 2 sides) CA 1977 Riesling 0 <0.02 87 4 70 0.13 CA 1976 Chardonnay 0 <0.02 87 4 58 0.27 (shanked 1.2 m band 2 sides) CA 1979 Alicante- 4 130 0.18 97 Bouche 4 130 0.21 4 130 0.18 CA 1979 Muscat of 4 131 0.26 97 4 131 0.15 4 131 0.10 (hand shaker 61 cm band 2 sides) CA 1979 Thompson 4 127 <0.02 97 Table 4. (con't) Interval between Location Year Variety Rate Treatment and Residues2/ Recovery lb a.i./A1/ Harvest (days) (mg/kg) (%) CA 1979 Emperor 4 106 0.04 CA 1980 Thompson 0 <0.02 73 4 105 0.11 4(20 G) 105 0.17 73 4 75 0.32 (3 shanks 30 cm apart in crop 7.6-10 cm) CA 1980 Thompson 0 <0.02 73 4 119 0.05 CA 1980 Rubired 0 <0.02 73 4 108 0.10 CA 1980 Thompson 0 <0.02 73 4 119 0.11 CA 1980 Tokay 0 <0.02 93 4 127 0.17 CA 1980 Tokay 0 <0.02 93 4 129 <0.02 Table 4. (con't) Interval between Location Year Variety Rate Treatment and Residues2/ Recovery lb a.i./A1/ Harvest (days) (mg/kg) (%) CA 1980 Thompson 0 <0.02 93 4 119 <0.02 CA 1980 Thompson 0 <0.02 93 4 125 0.09 4 125 0.11 1/ Treatment at maximum proposed rate of 4 lb a.i./A; 15g formulation except where indicated otherwise; 1 lb/A = 1.1 kg/ha. 2/ Corrected for recoveries shown. 3/ Said to be contaminated. 4/ Average of duplicate samples (0.48 and 0.49 mg/kg). Table 5. Concentration of Aldicarb Residues in Grape Processing Products or Related Products1/ Residue (mg/kg) Processed Residue Residue Range Concentration Factor Grape Number of Range in in Processed Product Samples Grapes Product Range Average Raisins 25 0.02-2.3 0.02-2.2 1-4.52/ 1.6 Pomace 163/ 0.04-3.3 0.03-3.1 0.5-2.34/ 1.15/ Fresh juice 17 0.04-3.3 0.02-1.8 0.5-2.46/ 0.9 Wine 13 0.04-3.3 0.02-2.37/ 0.2-0.77/ 0.48/ Stems 4 0.04-2.59/ 0.13-2.5 1-3.2 1.7 Raisin trash 7 0.02-0.3 0.9-2.810/ 1-2.411/ 2 lees 4 0.04-2.5 0.03-1.4 0.6-8.0 0.7 1/ Union Carbide 1982b. 2/ 2.5 or less except the 4.5 factor resulting from grapes with residues of 0.04 mg/kg. 7 of 25 a factor of 2 or greater. 3/ 7 pomace, 9 dry pomace. 4/ 5 of 16 a factor of 1.5 or greater. 5/ Regardless of whether "pomace" or dry pomace. 6/ All factors 0.9 or less except 2.5 factor. 7/ Excludes residues up to 3.6 mg/kg in first sediments. 8/ Excluding 3.1 apparent aberrant value. 9/ Two applications at label rate is not considered "good agricultural practice". 10/ High value treated according to proposed label 11/ Includes factors at 2.3, 2.4, 2.4. Table 6. Aldicarb Residues in Maize (Field Corn) Grain Interval Between Rate Treatment and Residue Location Year Variety lb a.i./A1/ Harvest (days) (mg/kg) Code2/ NC 1976 Golden 1.5 163 <0.01 C Harvest 163 <0.02 NC 1976 Golden 0 <0.01 Harvest 1.5 159 <0.01 0 <0.02 C 1.5 159 <0.02 C GA 1976 DeKalb 0 <0.01 XL-80 1.5 133 <0.01 1.5 133 <0.01 1.5 133 <0.01 1.5 133 <0.01 IA 1977 DeKalb 1.5 91 <0.02 K* XL-25 1.5 116 <0.02 K* 1.5 146 <0.02 1.5 146 <0.02 C IA 1977 DeKalb 1.5 77 0.04 K* 43A 103 <0.02 K* 133 <0.02 133 <0.02 C GA 1977 Funks 0 <0.02 G-4810 1.5 127 <0.02 MO 1977 Pioneer 1.5 125 <0.02 +* 3388 1.5 167 <0.02 1.5 167 <0.02 C MO 1977 Pioneer 0 <0.02 3388 1.5 156 <0.02 0 <0.02 C 1.5 156 <0.02 C OK 1977 DeKalb 0 <0.02 XL-75 1.5 158 <0.02 0 <0.02 C 1.5 158 <0.02 C Table 6 (con't) Interval Between Rate Treatment and Residue Location Year Variety lb a.i./A1/ Harvest (days) (mg/kg) Code2/ KS 1979 Pioneer 0 <0.02 3183 1.5 128 <0.02 IL 1979 B73 X 0 <0.02 M017 1.5 151 <0.02 CA 1980 Pioneer 0 <0.02 3541 1.5 126 <0.02 MO 1980 Pioneer 1.5 138 <0.02 3183 NC 1980 Coker 0 <0.02 1.5 134 0.03 MI 1980 NK, PX-7 0 <0.02 1.5 134 <0.02 NC 1980 Pioneer 0 <0.02 3184 1.5 143 <0.02 MS 1980 Trucker's 0 <0.02 Favorite 1.5 113 <0.02 IA 1980 Jacques 0 <0.02 JX-177 1.5 123 <0.02 IA 1981 Pioneer 0 <0.02 3780 1.5 151 <0.02 1.5 151 <0.02 1.5 151 <0.02 IA 1981 Pioneer 1.5 151 <0.02 3780 1.5 151 0.03 1.5 151 0.02 Table 6 (con't) Interval Between Rate Treatment and Residue Location Year Variety lb a.i./A1/ Harvest (days) (mg/kg) Code2/ Clayton 1981 Northrup 1.5 152 0.02 NC King <0.02 0.02 1981 Northrup 1.5 152 <0.02 King 0.23 <0.02 0 <0.02 CA 1981 XL-72AA 0 <0.02 1.5 175 <0.02 1.5 175 <0.02 1.5 175 <0.02 MS 1981 DeKalb 0 <0.03 XL-72B 1.5 119 <0.03 1.5 119 <0.03 1.5 119 <0.03 CO 1981 Pioneer 0 <0.02 3360 1.5 108 <0.02 1.5 108 <0.02 1.5 108 <0.02 TX 1981 Horizon 0 <0.02 870 1.5 87 <0.02 1.5 87 <0.02 1.5 87 <0.02 NM 1981 Funk 0 <0.02 G4449 1.5 78 <0.02 1.5 78 <0.02 1.5 78 <0.02 1/ Formulation: 15g; 1 lb/A = 1.1 kg/ha. 2/ Code: C : Cobs, with grain removed, sampled at maturity; K* : Green kernels samples before maturity; +* : Green kernels plus cobs sampled before maturity. All residues values with no code designation represent shelled grain sampled at maturity; : Less than All residue values include correction for recovery. 21 varieties, residues ranged from <0.01-0.23 mg/kg at 78 to 175 days after last treatment at the proposed rate. The 0.23 mg/kg appears to be aberrant since all other samples were 0.03 or less. Even at the same site and date, by either band or in-furrow application, five other replicates were < 0.02 mg/kg. Maximum residues on untreated samples were <0.03 mg/kg. Maximum residues were 0.04 mg/kg and 0.02 mg/kg on the few samples of cob and green kernels or green kernels plus cob, respectively. A limit of 0.05 mg/kg is supported for maize (field corn) grain. Forage Residues on 57 samples of maize (field corn) (whole green plants prior to maturity) ranged from <0.02 mg/kg - 11 mg/kg in 17 trials at 60 to 103 days after treatment. The results are summarized in Table 7. Residues from one location (Clayton, NC) are generally higher than other locations, even within the same state. At this location, residues ranged from 0.6 - 11 mg/kg and averaged 3.5 mg/kg from 18 samples in 6 trials. High apparent residues (up to 4.8 mg/kg) in untreated samples in two of the trials suggest possible contamination of untreated samples or analytical problems. Disregarding data from this location, residues on the remaining 49 samples ranged from <0.02 - 1.6 mg/kg. The 1.6 mg/kg value and the next higher residue at 1.3 mg/kg, under some assumptions, might be considered outliers since the next highest value without the Clayton, NC, studies would be 0.34 mg/kg. A limit of 10 mg/kg is supported (20 mg/kg on a dry weight basis). In 43 samples of maize (field corn) fodder (stover, or whole stalks, with ears removed) at maturity, residues ranged from <0.02-1.6 mg/kg at 87-175 days after treatment (Table 8). As in the case of forage, residues from the one location (2 trials, 6 samples with residues ranging from 0.07-1.6 mg/kg) were generally higher than other locations for which the residue range was <0.02-0.9 mg/kg, However, the difference is not as great and the control value from that location was typical of other locations (<0.02 mg/kg). If a separate limit is proposed for fodder, a 2 mg/kg limit is supported. The analytical method was validated on ears and shucks with 98% recoveries at fortification levels of 0.08-0.09 mg/kg. During field trials, recoveries generally ranged from 72-113% for grain, forage and fodder. Pecans Good agricultural practice information and residue data were available from one country. Data reasonably reflect the recommended single application at a rate of 5-10 lb. a.i./acres (5.5-11 kg/ha), method of application (two 1.2-1.8m bands on two sides of tree row at Table 7. Aldicarb Residues in Maize (Field Corn) Forage Interval between Rate1/ Treatment and Residue2 Location Year Variety lb a.i./A Harvest (days) (mg/kg) IA 1977 DeKalb 1.5 91 0.19 XL-25 116 IA 1977 DeKalb 1.5 77 1.6 43A 103 0.34 CA 1980 Pioneer 0 <0.02 3541 1.5 70 0.21 0 <0.02 1.5 100 0.06 MO 1980 Pioneer 0 <0.02 3183 1.5 102 0.03 MI 1980 NK, 0 <0.02 PX-7 1.5 77 0.03 NC 1980 NC 1.5 111 <0.02 MS 1980 Trucker's 0 <0.02 Favorite 1.5 71 0.05 IA 1980 Jacques 0 <0.02 JX-177 1.5 81 0.12 1.5 97 0.09 IA 1981 Pioneer 1.5 61 0.15 3780 1.5 61 0.19 1.5 61 0.03 0 <0.02 1.5 81 1.3 1.5 81 0.08 1.5 81 0.05 1.5 101 0.03 1.5 101 0.12 1.5 101 0.04 Table 7 (con't) Interval between Rate1/ Treatment and Residue2 Location Year Variety lb a.i./A Harvest (days) (mg/kg) IA 1981 Pioneer 1.5 61 0.07 3780 1.5 61 0.32 1.5 61 0.20 1.5 81 0.02 1.5 81 0.02 1.5 81 0.03 0 <0.02 1.5 101 0.05 1.5 101 0.04 1.5 101 0.04 MS 1981 DeKalb 1.5 61 0.11 XL-72B 1.5 61 0.17 1.5 61 0.13 0 <0.03 1.5 84 0.08 1.5 84 0.05 1.5 84 0.09 1.5 103 0.03 1.5 103 0.08 1.5 103 <0.03 Clayton 6/2/81 Northrup 1.5 60 4.2 NC King 9.1 6.6 6/22/81 Northrup 1.5 80 4.4 King 9.9 3.6 0 (control) 4.8 7/12/81 Northrup 1.5 100 0.66 King 1.3 1.9 Table 7 (con't) Interval between Rate1/ Treatment and Residue2 Location Year Variety lb a.i./A Harvest (days) (mg/kg) Clayton 6/2/81 Northrup 1.5 60 1.3 NC King 1.5 1.2 6/22/81 Northrup 1.5 80 3.1 King 2.7 1.6 7/12/81 Northrup 1.5 100 1.3 King 11 0.71 0 0.60 1/ Residues in whole, green plants prior to maturity; Formulation: 15 g;1 lb/A = 1.1 kg/ha. 2/ All residue values corrected for recovery. bud break) and normal interval from application from five states of the U.S. as summarized in Table 9 (Union Carbide 1982c and 1982d). Substantially more recent data were available, but did not reasonably reflect recommended usage or available information did not permit such a determination. In those cases summarized in Table 9 where the method of application did not closely follow label directions, residues would be expected to equal if not exceed those resulting from the recommended method. At recommended application rates, residues in kernels ranged from <0.01-0.27 mg/kg. Although the 0.27 value (uncorrected for 80-90% recoveries and an average of 0.22 and 0.32) resulted from applications on four sides of the tree instead of two; good agricultural practice was reasonably followed. Corrected for recovery, a maximum residue approaching 0.4 mg/kg could reasonably be expected on occasion, although in most cases residues could be expected to be < 0.3 mg/kg. Controls were generally <0.01 and 0.02 for kernels and shells respectively. A 0.5 mg/kg limit can be supported for kernels. Table 8. Aldicarb Residues in Maize (Field Corn) Stover (Fodder) Interval Between Location Year Variety Rate1/ Treatment and Residue2/ lb a.i./A Harvest (days) (mg/kg) NC 1976 Golden 1.5 163 0.04 Harvest NC 1976 Golden 1.5 159 0.04 Harvest IA 1977 DeKalb 1.5 146 0.04 XL-25 IA 1977 DeKalb 1.5 133 0.07 43A GA 1977 Funks 0 <0.02 G4810 1.5 127 <0.02 MO 1977 Pioneer 1.5 167 <0.02 3388 MO 1977 Pioneer 0 <0.02 3388 1.5 156 <0.02 OK 1977 DeKalb 0 <0.02 XL-75 1.5 158 0.05 KS 1979 Pioneer 0 <0.02 3183 1.5 128 0.03 IL 1979 B73X 0 0.07 M017 1.5 151 0.09 CA 1980 Pioneer 0 <0.02 3541 1.5 126 0.15 MO 1980 Pioneer 0 <0.02 3183 1.5 138 <0.02 NC 1980 Coker 0 <0.02 1.5 134 <0.02 NC 1980 Pioneer 0 <0.02 3184 1.5 143 0.03 Table 8 (con't) Interval Between Location Year Variety Rate1/ Treatment and Residue2/ lb a.i./A Harvest (days) (mg/kg) MS 1980 Trucker's 0 <0.02 Favorite 1.5 113 0.07 IA 1980 Jacques 0 <0.02 JX-177 1.5 123 <0.02 IA 1981 Pioneer 0 0.02 3780 1.5 151 0.02 1.5 151 <0.02 1.5 151 0.02 IA 1981 Pioneer 1.5 151 0.02 3780 1.5 151 <0.02 1.5 151 <0.02 Clayton 9/2/81 Northrup 1.5 152 0.22 NC King 0.07 0.17 9/2/81 Northrup 1.5 152 0.02 King 1.6 0.06 0 <0.02 CA 1981 XL-72AA 0 0.16 1.5 175 0.90 1.5 175 0.33 1.5 175 0.54 MS 1981 DeKalb 0 <0.03 XL-72B 1.5 119 <0.03 1.5 119 <0.03 1.5 119 <0.03 CO 1981 Pioneer 0 <0.03 3360 1.5 108 <0.03 1.5 108 0.03 1.5 108 0.05 Table 8 (con't) Interval Between Location Year Variety Rate1/ Treatment and Residue2/ lb a.i./A Harvest (days) (mg/kg) TX 1981 Horizon 0 <0.02 870 1.5 87 0.05 1.5 87 <0.02 1.5 87 <0.02 NM 1981 Funk 0 <0.02 G449 1.5 78 <0.02 1.5 78 0.03 1.5 78 0.02 1/ Residues in whole stalks, with ears removed, at maturity; Formulation: 15 g; 1 lb/A = 1.1 kg/ha. 2/ All residue values corrected for recovery. In shells (a feed item) residues are concentrated an average of about four times more than in kernels. Maximum residues were 1.1 mg/kg in shells from the maximum recommended application rate. A limit of 1 mg/kg should be adequate, if a limit is required. Some residue data for green nuts were also available. Generally, residues in green hulls were approximately twice that on immature shells and that on immature shells about twice that on kernels. No clear or consistent relationship can be drawn between immature and mature kernels, both being higher or lower at times. Recoveries of aldicarb sulphoxide and sulphone were 84% and 94% respectively in kernels fortified at 0.02-0.09 mg/kg. Similar recoveries were attained for shells (a feed item) fortified at 0.04-0.35 mg/kg. A realistic limit of determination of 0.02 mg/kg can be attained for both kernels and shells. Potatoes The Meeting previously estimated a maximum residue level of 1.0 mg/kg for aldicarb in potatoes (FAO/WHO 1980b). At its 14th Session, the CCPR recommended a limit of 0.5 mg/kg based on information that some countries had revised their GAP to permit lower MRLs and because some delegations objected to the 1.0 mg/kg limit, which had been under discussion. Table 9. Total Aldicarb Residues in Pecans at Harvest Interval after Aldicarb Residues2/ (mg/kg) Rate1/ last Location Year lb a.i./A Application Kernels Shells Whole Nut Georgia (Calculated) 1976 2 197 0.02 0.04 0.03 4 0.04 0.13 0.08 6 0.07 0.20 0.13 8 0.09 0.51 0.30 10 0.11 0.12 0.12 10 183 0.10 0.27 0.17 20 0.12 0.55 0.32 5 + 5 106 0.17 0.50 0.33 1975 2 180 0.01 0.03 0.02 4 0.02 0.06 0.04 6 0.01 0.04 0.02 8 0.03 0.09 0.05 10 0.01 0.05 0.03 1976 5-6 188 0.06 10 185 0.27 20 0.16 1975 9.6 ca. 180 0.03 19.2 0.04 (average of replicates) 38.4 0.13 Alabama 1976 5 171 0.08 10 0.05 South Carolina 1976 5 181 0.05 0.61 0.32 10 0.12 1.1 0.60 20 0.30 1.7 0.97 1976 5 268 0.01 0.02 0.02 10 0.01 0.04 0.03 Table 9 (con't) Interval after Aldicarb Residues2/ (mg/kg) Rate1/ last Location Year lb a.i./A Application Kernels Shells Whole Nut Mississippi 1976 6 189 0.01 12 0.13 24 0.08 New Mexico 1979 2 169 0.04 133 <0.02 2.5 169 <0.02 <0.02 133 0.09 0.17 1/ 1 lb/A = 1.1 kg/ha; 2/ Uncorrected for recoveries of 80-90%; 3/ Closely approximate recommended 4-6 ft, (1.2-1.8 m) band on two sides of the tree row. The 1982 JMPR was informed that aldicarb is registered for use on potatoes in 32 countries although good agricultural practice information was provided to this Meeting only for the Netherlands, South Africa and the U.S. (Table 2). Also provided were previously submitted and new residue data, mostly from the U.S. (some Canadian), where aldicarb application rates on potatoes have been revised downward and other restrictions imposed. Residue data were available from well over 600 samples from Canada and 24 states in the U.S. for the period 1964-1979 and represent application rates from 1-3 lb a.i./A (1.1 - 3.3 kg/ha) either at planting, after planting or split applications. Approximately 40% of data were new. Residues in 144 untreated controls ranged from <0.01 to 0.11 mg/kg. The data are too numerous for a detailed summarization. Data from 240 samples treated at time of planting at a rate of 2.3 lb a.i./A (2.2-3.3 kg/ha) with granular formulations (10G, 10GV, 10G-1968 or 15 G) and a minimum of 90 days (GAP) are summarized in Table 10 (Union Carbide 1982e and 1982f). Sixteen of the 240 exceeded 0.5 mg/kg. Five of the 16 were from Canada at 90-91 days after planting (DAP) on immature tubers. Four of the five were >1 mg/kg. Eight of the 16 were on the Pungo variety grown in Virginia, three of which were on immature potatoes (90-101 DAP) and the rest were on immature potatoes. Table 11 summarizes residues > 0.5 mg/kg on mostly immature potatoes treated at 2-3 lb a.i./A (2.2-3.3 kg/ha) at planting for the 60-89 DAP interval. The 26 values are from a total of 41 at this interval and application rate. Most of these approach or exceed 1.0 mg/kg. Again, Canadian data are noticeably and inexplicably higher. Data on the Pungo variety from one site in Virginia again tend to be higher than other varieties in other states. Data were unavailable for other varieties or sites in Virginia or the Pungo variety in other states. Data were also available for 63 samples treated at rates of < 2 lb a.i./A (2.2 kg/ha) (all <0.5 mg/kg) and for 65 treated at >3 lb active/A (3.3 kg/ha) and a 90 DAP minimum. For the latter, residues ranged from <0.5 mg/kg on 46 samples, 0.5-1.0 mg/kg on 9 and >1 mg/kg on 10. These are of less importance for estimating residue levels as they do not reflect good agricultural practices reported to this Meeting, except those from South Africa (no residue data were available). Eighty potato samples were available from post-plant sidedress applications from 0.5 - 11 lb a.i./A (0.55-12 kg/ha) and days after last application ranging from 25-175. All residues were <0.5 mg/kg. Although no information on registered uses permitting split applications to potatoes was available to the Meeting, residue data were available and are summarized for 100 samples in Table 12. These data suggest that residues would not exceed 0.5 mg/kg if a 1-2 lb a.i./A (1.1-2.2 kg/ha) application at planting is followed by a 1-2 lb (1.1-2.2 kg/ha) post-planting sidedress and a 90-day interval from last application to harvest is observed. The 1.0 mg/kg level previously estimated was based on a 120-day interval from last application to harvest. Good agricultural practices reported to this Meeting permit harvest at 90 days and 6.7% of samples treated in the U.S. and Canada at 2.3 lb a.i./A (2.2-3.3 kg/ha) at the 90-day interval or longer exceeded 0.5 mg/kg. The 1.0 mg/kg limit is confirmed. Table 10. Total Aldicarb Carbamate Residues in Potato Tubers; a Minimum of 90 Days Following Application of Granular Formulations Residue Levels From Residue Levels From 2-2.5 lb a.i/A At Planting (mg/kg)1/ 2-75- 3.0 lb a.i./A at Planting (mg/kg) 0.01 - 0.11- 0.21- 0.31- 0.41- 0.10- 0.11- 0.21- 0.31- 0.41- Location <0.01 0.10 0.20 0.30 0.40 0.50 >0.51 <0.01 0.10 0.20 0.30 0.40 0.50 >0.51 TOTAL Canada 4 1 1 52/ 11 U.S.: North Dakota 1 6 2 9 18 Oregon 2 1 3 Washington 2 1 4 2 1 10 Arizona 5 1 1 7 California 2 16 7 6 2 33 Colorado 1 1 1 2 1 6 Connecticut 1 1 Delaware 1 1 2 Florida 2 2 4 Idaho 3 1 17 5 2 1 1 13/ 31 Indiana 1 1 Maine 2 5 2 3 12 Michigan 1 1 10 2 14 Table 10 (con't) Residue Levels From Residue Levels From 2-2.5 lb a.i/A At Planting (mg/kg)1/ 2-75- 3.0 lb a.i./A at Planting (mg/kg) 0.01 - 0.11- 0.21- 0.31- 0.41- 0.10- 0.11- 0.21- 0.31- 0.41- Location <0.01 0.10 0.20 0.30 0.40 0.50 >0.51 <0.01 0.10 0.20 0.30 0.40 0.50 >0.51 TOTAL Minnesota 2 5 1 1 2 11 North Carolina 1 1 2 1 14/ 6 New Hampshire 1 1 2 New Jersey 1 1 2 New York 1 3 4 7 3 4 15/ 23 Ohio 2 5 7 Pennsylvania 1 1 Rhode Island 1 1 Texas 2 2 Virginia 2 2 1 56/ 2 1 2 1 37/ 19 Table 10 (con't) Residue Levels From Residue Levels From 2-2.5 lb a.i/A At Planting (mg/kg)1/ 2-75- 3.0 lb a.i./A at Planting (mg/kg) 0.01 - 0.11- 0.21- 0.31- 0.41- 0.10- 0.11- 0.21- 0.31- 0.41- Location <0.01 0.10 0.20 0.30 0.40 0.50 >0.51 <0.01 0.10 0.20 0.30 0.40 0.50 >0.51 TOTAL Wisconsin 3 5 2 3 13 Total 3 36 16 2 2 1 5 5 79 36 24 14 6 11 240 1/ 1 lb/A = 1.1 kg/ha; 2/ 4 of these 5 exceeded the 1.0 mg/kg tolerance; currently under investigation; rate = 3.0 lb a.i./A; 90-91 days following last application; 0.98, 1.1, 1.5, 0.83, mg/kg. Original studies unavailable; 3/ Rate = 3.0 lb a.i./A; 89 days following last application; Immature; 0.72 mg/kg; 4/ Rate = 3.0 lb a.i./A; formulation 10g-1968 trial conducted on Union Carbide farm; immature tubers; 91 days following last application; 0.82 mg/kg; 5/ Rate = 3.0 lb a.i./A; 100 days following last application; immature tubers; 0.54 mg/kg; 6/ Rate = 2.0 lb a.i./A; 1 sample from plot receiving 10GV formulation, 98 - 127 days following last application; immature 1; mature 4; Variety - Pungo; 0.76, 0.66, 0.53, 0.60, 0.97 mg/kg; 7/ Rate = 3.0 lb a.i./A; 90-101 days following last application; immature tubers; variety - Pungo; 0.69, 0.69, 0.69 mg/kg. Table 11. Aldicarb Residues in Potato Tubers Following Application at Planting of 10G or 15G Formulations Application rate Days After Location Variety (lb a.i./A)1/ Application Residue (mg/kg)2/ Canada Unknown 3 80 1.5, 2.4 3 85 1.6 3 79 3.4, 2.7, 2.5 3 84 2.4, 1.3, 2.1 U.S.: CA Kennebec 3 70 0.84 ID Russet 3 67 0.67 Burbank 3 89 0.72 NY Superior 3 81 0.62 ME Ketahdin 3 63 0.78 NC Maine Cobbler 3 57 0.98 NC Irish Cobbler 3 77 0.99 NC Irish Cobbler 3 61 3 NC Irish Cobbler 3 77 1.2 VA Pungo 2 66 2.9 VA Pungo 2 86 1.4 VA Pungo 2 66 0.73 VA Pungo 2 86 0.69 VA Pungo 2 86 0.72 VA Pungo 2 66 1.0 VA Pungo 3 70 1.5 VA Pungo 3 70 0.93 (sulphoxide) 1/ 1 lb/A = 1.1 kg/ha 2/ The 26 values above 0.5 mg/kg are from a total of 41 "at planting" applications at given application rate and interval. Samples were described as "immature tubers" except in two cases that were described as "tubers". Table 12. Residues in Potatoes Resulting from Supervised Trials Using Split Application of Aldicarb Granular Formulation Application Interval Following Rate Last Application Residue State (lb a.i./A)1/ (days) (mg/kg) CA 1.0 + 1.0 52 0.09 1.5 + 1.5 52 0.13 CT 2.0 + 1.0 124 0.022/ ID 1.5 + 1.5 128 0.07 3.0 + 3.0 120 0.04 3.0 + 3.0 133 0.15 ME 2.0 + 1.0 69 0.26 3.0 + 3.0 90 0.84 MI 1.5 + 1.5 94 0.15 NC 3.0 + 3.0 15 0.10 3.0 + 3.0 15 1.20 3.0 + 3.0 34 0.46 3.0 + 3.0 57 0.14 3.0 + 3.0 58 0.24 ND 1.5 + 1.5 75 0.03 NJ 1.5 + 1.5 93 0.01 1.5 + 1.5 106 0.05 NY 1.5 + 1.5 62 0.06 2.0 + 1.0 62 0.05 2.0 + 2.0 93 0.36 2.0 + 3.0 93 0.62 3.0 + 2.0 93 0.36 3.0 + 2.0 90 0.31 3.0 + 2.0 70 0.28 3.0 + 3.0 85 0.57 3.0 + 3.0 110 0.42 3.0 + 3.0 42 2.2 3.0 + 3.0 76 0.99 Table 12 (con't) Application Interval Following Rate Last Application Residue State (lb a.i./A)1/ (days) (mg/kg) 3.8-4.8 + 1.8-2.1 107 <0.01 " 109 0.29 " 72 0.41 " 86 0.29 " 106 0.29 " 110 0.25 " 90 0.34 " 106 0.47 " 73 0.35 " 88 0.37 " 108 0.46 " 108 0.46 " 108 0.34 " 107 0.40 " 109 0.25 " 73 0.24 " 87 0.20 " 108 0.20 " 108 0.21 " 108 0.17 " 108 0.61 " 108 0.25 " 69 0.41 " 84 0.52 " 103 0.52 " 72 0.63 " 86 0.31 " 107 0.86 " 85 0.70 " 110 0.54 " 42 1.40 " 76 0.97 4.0 + 3.0 85 0.58 " 110 0.48 " 42 2.10 " 76 1.30 4.5 + 4.2 90 0.43 " 108 0.47 Table 12 (con't) Application Interval Following Rate Last Application Residue State (lb a.i./A)1/ (days) (mg/kg) 5.0 + 2.1 74 0.17 " 89 0.11 " 108 0.23 " 110 0.59 " 110 0.59 " 108 0.46 " 109 0.19 " 85 0.90 " 110 0.61 " 85 0.79 " 110 0.61 " 42 2.2 " 76 1.0 6.0 + 2.1 103 0.54 OR 1.5 + 1.5 177 0.01 3.0 + 3.0 114 0.093/ " 114 0.113/ " 76 0.34 WA 0.9 + 1.4 104 <0.01 1.5 + 1.5 162 0.09 " 142 0.02 2.0 + 4.0 24 0.59 " 43 0.53 " 70 0.19 " 99 0.55 Table 12 (con't) Application Interval Following Rate Last Application Residue State (lb a.i./A)1/ (days) (mg/kg) WA 3.0 + 3.0 85 0.45 " 163 1.40 " 49 0.76 " 69 0.46 " 99 0.15 " 125 0.18 " 107 0.98 " 112 0.02 " 112 0.14 1/ lb/A = 1.1 kg/ha; 2/ First application 7 days preplanting; 3/ At emergence + sidedress. Sample totals: 1.0+1.0 - 1; 0.9 + 1.4-1; 1.5+1.5-10; 2.0+1.0-3; 2.0 + 2.0-1; 2.0 + 3.0-1; 2.0 + 4.0-4; 3.0 + 2.0-3; 3.0 + 3.0-24; 3.8-4.8 + 1.8-2.1-32; 4.0 + 3.0-4; 4.5+4.2-2; 5.0 + 2.1-13; 6.0+2.1-1. Sorghum Grain and Sorghum Fodder Aldicarb is said to be registered for use on sorghum in four countries; good agricultural practice information and residue data were available only for the U.S. (Union Carbide 1982c and 1982d). Forty-five grain samples from six states (1970-1980) were treated at planting at approximately the recommended 0.5-1 lb a.i./A (0.55- 1.1 kg/ha) rate and harvested at or near the normal harvest (92-170 days after treatment except for 4 at 75 days). Residues ranged from <0.01 to 0.13 mg/kg (0.025 mg/kg av.). Residues in fodder from 22 of these samples ranged from <0.01-0.4 mg/kg (av. 0.05 mg/kg). The residue distribution for the grain and fodder were: No. of Samples at each Residue Level Residue (mg/kg) Grain Fodder <0.02 37 16 0.02 0 1 0.03 3 1 0.04 3 0 0.05 0 1 0.06-0.08 0 0 0.09 1 1 0.10 0 0 0.13-0.14 1 1 0.4 0 1 45 22 At higher than recommended rates (1.53x) residues on 14 samples of grain ranged from <0.01-0.1 mg/kg (0.025 mg/kg av.) and on samples of fodder, <0.02-0.25 mg/kg (0.06 mg/kg av.). A minimal amount of data were available on milling products (see "Fate of Residues"). Considering that most of the residues were not corrected for recoveries of approximately 90%, maximum residue levels of 0.2 and 0.5 mg/kg respectively for sorghum grain and fodder can be supported. Some residue data were also available for green forage with a maximum residue of 12.4 mg/kg at 40 days after a 1.2 lb a.i./A (1.3 kg/ha) treatment at planting. This declined to 0.17 and 0.05 mg/kg at 68 days and at harvest respectively. Other studies showed similar declines. However, because of potential danger to animals, feeding or foraging prior to grain harvest is not considered good agricultural practice in the U.S. Analytical recoveries of aldicarb residues were generally > 90% in sorghum grain and fodder at fortification levels of 0.04-2.2 mg/kg. The limit of determination is approximately 0.02 and 0.04 mg/kg for grain and forage respectively. Sugarcane The Meeting was informed that aldicarb is registered for use on sugarcane in 26 countries. Good agricultural practice information was available for Argentina, Brazil, South Africa and the U.S. Residue data were available mostly from the U.S. and South Africa and some from India, Indonesia and Pakistan. A 120-day preharvest interval is imposed in the U.S. for a single application at planting. Normal harvest may be as soon as 6.5 months for first or second stubble crops or approximately 12-14 months for some autumn plantings. No information on preharvest intervals was available for countries other than the U.S. A summary of U.S. and Puerto Rico residue data in given in Table 13 (Union Carbide 1982c and 1982d). Residues on stalks at 123 days or longer in the U.S. ranged from <0.01 mg/kg to 0.02 mg/kg when applications were 0.6-1.3 × the maximum recommended application rate, even with a split application. Untreated controls were < 0.01 mg/kg. Residues for sugarcane leaf samples under similar conditions ranged from 0.04-0.19 mg/kg (av. 0.09). Residues at harvest would normally be expected to be less than the maximum value that resulted from 1.3 × the maximum application rate and 123 days after last application, since a more typical interval is at least 180 days. Untreated controls for leaves were also 0.02 mg/kg. Data on sugarcane from Puerto Rico at similar application rates and longer intervals were noticeably higher, ranging from 0.03- 0.07 mg/kg. Untreated samples were also higher, ranging from 0.02- 0.05 mg/kg, although the sensitivity was said to be 0.02 mg/kg. A substantial amount of additional data were available from other countries, but most of the application rates and days after last treatment were not representative of GAP. One study from South Africa, which was representative of GAP (Union Carbide 1982d) showed residues of <0.02 mg/kg at 321 days in stalks/leaves from application of a 10G formulation at 3.3 kg a.i./ha. In another, in India (Union Carbide 1982d) residues in stalks at 185 days after treatment at 1.5, 2, 3 and 4 kg a.i./ha were <0.04, 0.04, 0.045 and 0.077 mg/kg respectively. The colorimetric analytical method used had a sensitivity of only 0.04 mg/kg. Because the Indian data were determined by methodology with limited sensitivity, the U.S. data are more pertinent for estimating maximum residue levels. Maximum residues resulting from recommended application rates were, therefore, 0.03 mg/kg from the Puerto Rican studies where untreated controls had residues up to 0.05 mg/kg. Levels in untreated sugarcane controls have been observed at this level or higher in other studies (Table 14) although in this case there is some suggestive evidence of contamination. Maximum residue levels of 0.03 and 0.2 mg/kg respectively for sugarcane stalk and fodder/forage are reasonable for application rates up to 3.4 kg a.i./ha and a 180-day preharvest interval. Data were insufficient for an estimate of residues in bagasse (see "Fate of Residues"). Table 13. Total Aldicarb Residues in Sugarcane Stalks and Leaves Experimental Rate of Interval from Residue Found Station and Treatment1/ last Treatment Location (lb a.i./A) Application to Sampling Stalk Leaves (days) mg/kg mg/kg Louisiana 2.0 Side-dress 2 sides to 35 0.05 0.28 ratoon cane Belle Rose 1970 64 0.10 0.66 64 0.15 1.26 89 0.06 1.02 123 0.01 0.04 216 0.01 2.0 Side-dress 35 0.05 0.26 2 sides to 64 0.12 1.11 ratoon cane 89 0.01 0.18 123 0.02 0.05 4.0 Side-dress 35 0.14 0.86 2 sides to 64 0.18 1.36 ratoon cane 89 0.03 0.30 123 0.01 0.08 216 0.01 4 Side-dress 64 0.01 0.02 2 sides to 64 0.01 0.02 ratoon cane 89 0.05 0.65 123 0.02 0.19 Untreated 35 0.01 0.02 Untreated 64 0.01 0.02 Untreated 89 0.01 0.02 Table 13 (con't) Experimental Rate of Interval from Residue Found Station and Treatment1/ last Treatment Location (lb a.i./A) Application to Sampling Stalk Leaves (days) mg/kg mg/kg Baton Rouge 4.0 Banded and 392 <0.01 (1968) rototilled 392 <0.01 392 <0.01 392 <0.01 Untreated <0.01 2.0 Banded and 378 <0.01 (1969) incorporated at planting Louisiana 1.5 lb+1.5 lb2/ In-furrow at 189 0.01 planting plus side dress Untreated2/ 0 0.01 3 lb + 3 lb In-furrow at 189 0.01 planting plus side dress Florida 70-71 2 lb 36 cm Band incorporated 363 0.01 at planting 4 lb 36 cm Band incorporated 363 0.01 at planting Table 13 (con't) Experimental Rate of Interval from Residue Found Station and Treatment1/ last Treatment Location (lb a.i./A) Application to Sampling Stalk Leaves (days) mg/kg mg/kg Untreated - 0 0.01 2 lb 36 cm Band covered 242 0.01 at off-bar with 2.5 cm soil (side-dress). 4 lb 36 cm Band covered 242 0.01 at off-bar with 2.5 cm soil (side-dress). Untreated 0.01 Puerto Rico 2 0.03 44 (1979) 3 row 300 0.03 42 row 300 0.04 43 row 300 0.05 44 4 row 300 0.07 42 4 row 300 0.05 43 4 row 44 Untreated 0.04 42 0.05 43 0.02 44 1/ 1 lb/A = 1.1 kg/ha; Formulation - 10G; 2/ Treated 9/18/72 and 3/15/73. Table 14. Total Aldicarb Residues in Sugarcane Stalks, South Africa, 1970 Rate Residues (mg/kg) (lb a.i./A)1/ 6 Days 14 Days 21 Days2/ 27 Days 35 Days 56 Days 90 Days 2.5 0.22 0.31 0.22 0.05 0.11 0.02 <0.02 5.0 0.34 0.90 0.29 0.15 0.23 0.03 <0.02 7.5 0.84 1.12 0.52 0.27 0.29 0.06 <0.02 10.0 1.18 1.20 0.61 0.28 0.57 0.08 <0.02 Control 0.08 0.02 <0.02 <0.02 0.08 <0.02 <0.02 Control3/ <0.02 <0.02 <0.02 <0.02 1/ Broadcast and incorporated at planting (TEMIK 10g); 1 lb/A = 1.1 kg/ha; 2/ Irrigated during this period; 3/ Controls outside experimental area. Studies from outside the U.S. also confirm the U.S. data, which shows that residues in the leaves may be approximately 2-10 times that in the stalk. One of these studies from South Africa (Table 14) clearly shows residues peaking at 14 days after treatment with a subsequent rapid decline. Other studies have shown similar rapid dissipation of residues, although the period for peaking in leaves and stalks had been as much as 50 days (Union Carbide 1982c). Except for the Indian data, as noted, recoveries were generally > 80% in stalk and leaves at fortification levels of 0.01 and 0.02 mg/kg in each respectively. Recoveries were somewhat lower from juice and bagasse. The Indian data were based on the same basic procedure, except that determination was by colorimetry instead of gas chromatography. The sensitivity was 0.04 mg/kg. Sweet Potatoes Good agricultural practice information was available from three countries (Table 2) and reportedly used in at least one other. Residue data (uncorrected for 90% analytical recoveries) were available only from the U.S., but from six states. Those studies representing GAP are summarized in Table 15 (Union Carbide 1982c). Table 15. Aldicarb Residues in Sweet Potatoes at Harvest from Supervised Trials1/ Interval Rate (lb a.i./A)2/ Location Year to Harvest (days) 1 2 3 4 5-6 Louisiana 1968 126 <0.01 <0.01 <0.01 1969 125 <0.01 1973 110 <0.01 0.01 0.02 1976 128 <0.01 <0.01 North Carolina 1974 127 <0.01 <0.01 0.02 1976 114 0.01 0.04 1973 146 0.02 0.03 South Carolina 1975 156 (3 varieties) 0.01 Virginia 1974 119 0.04 119 0.05 0.16 119 0.11 1975 122 0.05 0.05 0.09 122(3 replicates) 0.03 Oklahoma 1974 157 <0.01 0.02 California 1976 149 0.10 1/ Uncorrected for 90% recoveries. 2/ Recommended rate is 2-3 lb a.i./A (2.2-3.3 kg/ha); Formulation, 10 G. These data indicate that residues in sweet potatoes following the recommended application rate should not exceed 0.1 mg/kg at the normal harvest interval of approximately 120 days after a single application at planting. Residues in untreated controls were <0.01-<0.02 mg/kg. Additional data were provided to the Meeting for immature sweet potatoes from three states, which had treatments at planting at higher than recommended and recommended application rates, 15 to 30 days before normal harvest. Residues in 12 samples that had been treated at recommended rates ranged from <0.01-0.19 (av. 0.07 mg/kg for seven samples) when harvested 30 days before normal harvest and <0.01- 0.08 mg/kg (av. 0.05 mg/kg for 5 samples) at 15 days before normal harvest. Maximum residues on these 12 samples were 0.05 mg/kg at normal harvest. In sweet potatoes vines residues in two states following recommended application rates were <0.04, 0.89; 0.04, 0.21 and <0.04, 0.34 mg/kg at 30 days and 15 days before and at normal harvest respectively. Residues were significantly higher at higher than recommended rates. Residues could approach 1.0 mg/kg. The feeding of vines from aldicarb treated sweet potatoes is prohibited in the U.S. A 0.1 mg/kg limit for aldicarb in sweet potatoes can be supported. This is less than the current or proposed limit for potatoes, but reflects different GAP. When sweet potatoes were fortified at 0.02-0.22 mg/kg, recoveries were 92, 88 and 97% for aldicarb, its sulphoxide and sulphone respectively. A realistic limit of determination for sweet potatoes is 0.01 mg/kg. Carcase Meat and Milk The current 0.01 mg/kg limit for carcase meat and 0.002 mg/kg for milk (at or about the limits of determination) are based on the potential for residues resulting from those feed items on which maximum residue levels were estimated. Of the feed items considered at this Meeting, potential for residues in animals (cattle) is greatest for maize. The potential from grain is not so great, as the residues are low, hub from forage/ fodder, where residues can be up to 10 mg/kg, an increased potential does exist. Assuming that a possible 50% of the cattle diet could be forage/fodder residues in the diet could be 5 mg/kg from the fodder/forage alone. If other feed items, such as grape pomace or citrus pulp, bearing aldicarb residues near proposed tolerance levels are fed at the same time, dietary levels of 6-7 mg/kg could theoretically exist. Based on one feeding study at 5 mg/kg in the diet previously examined by this Meeting (Romine 1973), no detectable residues (<0.01 mg/kg) would result in meat and <0.002 mg/kg in milk from 5 mg/kg in the diet. From another study (Dourough et al 1970) carbamate residues of approximately 0.008 mg/kg can be estimated in liver from a dietary feeding level of 1.2 mg/kg. This would be 0.03 mg/kg, translated to a 5 mg/kg dietary level. From the same study, translating the 0.002 mg/kg residues in milk to a 5 mg/kg dietary level would result in residues of 0.01 mg/kg, which is, incidentally, the limit recommended by the 14th Session of the CCPR. Therefore, because of the increased potential for residues in carcase meat and milk, another feeding study at a higher feeding level is needed. Maize may contribute up to 70% of the diet of poultry, which could result in a dietary intake of 0.035 mg/kg with 0.05 mg/kg in grain. A greater potential for residues, however, could come from sorghum grain (up to 60% of the diet), for which a 0.2 mg/kg residue level is estimated. Based on poultry feeding studies previously reviewed by this Meeting (Hicks et al 1972) maximum aldicarb equivalent residues in poultry were found in liver at 0.14 mg/kg after feeding 1.0 mg/kg in the diet for 21 days. Based on this and similar data for eggs, any residues in poultry meat or eggs would be expected to be less than the 0.01 mg/kg limit of determination. FATE OF RESIDUES In Plants Although the fate of aldicarb in plants has been previously reviewed (FAO/WHO 1980b), some additional information was provided to this Meeting. When the ratio of aldicarb sulphoxide to sulphone was studied in sugarcane plants, the ratio declined from approximately 8 at 35 days after last application to approximately 1.7 after 123 days (Union Carbide 1982c). In Storage and Processing Grapes Data were available for grape products from simulated commercial processing of grapes with field incurred residues and are summarized in Table 5 (Union Carbide 1982b). There appears to be no appreciable concentration of aldicarb in fresh grape juice and wine. There can be appreciable concentration in pomace, raisin trash and apparently in stems, although data are insufficient for the latter to permit a firm conclusion on the amount. The actual residues on stems in Table 5 do not represent GAP, since two applications were made. The proposed label permits only one. From Table 5, a concentration factor of 2.5 would appear to be reasonable for estimating maximum residues in raisins and pomace from residues in grapes. This factor is somewhat lower than the theoretical concentration factor of approximately 4x for raisins, but is supported by the data. Actual residues for raisin trash represent GAP. Grape samples with field incurred residues from 0.15-4 mg/kg showed no appreciable change in the level of residue after storage at -10°F (-23°C) for 16 to 18 months. Maize The distribution of average aldicarb residues in endosperm (meat), hulls, and oil (germ) were 0.01, 0.034 and 0.005 mg/kg respectively from dry milled grain with field incurred residues of approximately 0.014 mg/kg (Union Carbide 1982a). Recoveries were > 81% at 0.025-0.05 mg/kg fortification levels. Untreated controls gave residues of < 0.005 mg/kg. Although grain samples with residues further removed from levels near the limit of determination (approximately 0.02 mg/kg for oil) would have been preferred, the study does suggest concentration in hulls only and at approximately 2.5 times. Additional processing studies at higher residue levels would be useful to further elucidate potential residues in processed products of maize. Sorghum Minimal data on the effects of milling on residues in sorghum grain were available (Union Carbide 1982c) and are summarized below: Residue (mg/kg) grain bran shorts flour 0.09 0.41 0.05 0.03 0.04 0.04 0.02 <0.02 As in the case of maize, these data are inadequate to draw firm conclusions on possible residue concentrations during processing. Additional processing studies from grain with higher initial residues are desirable. When crops with field-incurred residues in sorghum grain of 0.1-0.11 mg/kg and fodder of 0.14-0.25 mg/kg were stored for 10 months at -10°F losses were about 10% for grain and 27% for fodder. Sugarcane When sugarcane stalk and leaves with residues of 0.018, 0.22 and 0.26, 0.19 mg/kg respectively were held in storage at -15°C for up to 221 days, no losses in residues occurred. In fact, apparent unexplained increases on the order of 30% were found (Union Carbide 1982c). When sugarcane stalks containing field incurred residues of <0.011 mg/kg were processed in a pilot unit, no measurable residues were detected in bagasse, dilute juice, syrup, raw sugar or molasses (Union Carbide 1982c,d). When dilute juice was fortified at 0.24 mg/kg, residues were 0.1, 0.21, <0.011 and 0.034 mg/kg respectively in clarified juice, syrup, raw sugar and molasses (Union Carbide 1982c). Because the stalk residues were so low, a firm conclusion cannot be drawn for concentration of residues in juice or bagasse. METHODS OF RESIDUE ANALYSIS The analytical methods used for the supervised trials considered by this Meeting are basically the same as those examined previously (FAO/WHO 1980b). They are for the most part based on a 3:1 acetone:water extraction, oxidation of aldicarb residues to the sulphone and determination by flame photometric gas liquid chromatography. Milk As a result of discussions at the 1982 Meeting of the CCPR on the limit of determination for aldicarb in milk, the manufacturer re-submitted the analytical method (Lykins 1969). The CCPR considered 0.01 mg/kg to be a more realistic limit of determination than the 0.002 mg/kg estimated by the JMPR. The method is similar to other variations of the basic method for aldicarb in crops, but includes a phosphoric acid precipitation step before oxidization of aldicarb residues to the sulphone. The manufacturer validated the method by analysing milk samples fortified from 0.0011 to 0.044 mg/kg with individual components of the aldicarb residue. Recoveries ranged from 76.2 to 121% with average recoveries being 91.3%. Both the CCPR and this Meeting were informed that the U.S. Environmental Protection Agency had validated the same basic method UC 21149-III Milk, entitled: "Determination of Total Toxic Residues in Milk by Gas Chromatography". Validations were conducted with fortifications at 0.002 and 0.004 mg/kg sulphoxide, with recoveries ranging from 60-100% (79% av.) at the 0.002 mg/kg level. No major difficulties were encountered and no interferences were found at the retention of the sulphone. The limit of detection was estimated at 0.0005 mg/kg. NATIONAL MAXIMUM RESIDUE LIMITS The Netherlands reported to the Meeting the following revisions of and additions to their 1979 submission: Commodity mg/kg Brussels sprouts 0.05 Onions 0.1 Potatoes 0.3 Other food commodities 0 (0.02) The 0.05 mg/kg limit for Brussels sprouts is at or about the limit of determination. In "other commodities", no residues are permitted, the limit of determination being 0.02 mg/kg. APPRAISAL The Meeting examined residue data for several commodities not considered previously, as well as substantial additional data for citrus and potatoes. Data on the latter two resulted from discussions at the Codex Committee on Pesticide Residues. Additional information on the fate of residues and the analytical limit of determination for milk was also examined. Good agricultural practice (GAP) information was provided for some commodities for which residue data were available and only proposed GAP information was available for others. Data for Brussels sprouts were inadequate for estimating a maximum residue level. Data were adequate for estimating residue levels for maize (grain), maize fodder/forage, pecans, sorghum grain, sorghum fodder and sweet potatoes, and for confirmation of the limit for potatoes and citrus. In citrus, the Meeting examined new data in conjunction with substantial data previously reviewed. Except for one sample (out of 600) with a residue of 0.22 mg/kg harvested 199 days after treatment, all samples with residues > 0.2 mg/kg resulted from preharvest intervals of 61 days or less. The current 0.2 mg/kg limit is based on a 90-day preharvest interval. However, the Meeting received new information that a 30-day preharvest interval is good agricultural practice for lemons. Available data on Valencia oranges and limes, reflecting recommended application rates and preharvest intervals of 30-61 days, give indirect evidence that under some good agricultural practice conditions residues in lemons could exceed 0.2 mg/kg, possibly approaching 0.5 mg/kg. While the Meeting concluded that the 0.2 mg/kg can be confirmed, it also concluded that additional residue data on lemons are highly desirable to give added assurance that the 0.2 mg/kg limit is adequate. The Meeting was informed that consideration will be given to conducting additional studies to provide that assurance. In grapes, many of the treatments did not closely follow proposed uses or insufficient information was available to make that determination. For this reason, limits were not estimated. Residues from supervised trials at least partially consistent with proposed uses and harvest at intervals greater than or approximately the recommended 120-day interval between harvest and last treatment gave a maximum residue of 0.49 (a duplicate analysis that would appear to be a little higher relative to similar samples, but there is no basis for discarding it). Lower values on other samples from the same cooperator cannot be directly compared since the type of treatments were different. Additional supervised trials strictly following recommended application and last treatment to harvest interval are needed for grapes. Also needed is information on nationally approved agricultural practices. In maize (field corn) forage, data from one geographical area are substantially higher than those from other areas, but there is no firm basis for discounting the substantial amount of data from this area. In potatoes, a lot of additional data were examined along with the substantial amount of data previously examined by the Meeting. A significant number of trials representing current GAP resulted in residues exceeding 0.5 mg/kg. A few of these samples were on "immature" tubers, variety Pungo, or were inexplicably higher than even the previous JMPR maximum residue level estimate of 1.0 mg/kg. Too much emphasis cannot be attached to "immature" tubers since these may also be harvested, marketed and consumed. With all factors taken into account, the Meeting concluded that the available data continue to support the previously estimated limit of 1.0 mg/kg, while recognizing the preference of the Codex Committee on Pesticide Residues for a 0.5 mg/kg limit. In sugarcane, substantial data were available, but no residue level is recommended since sugarcane is not considered a major item in international trade. Studies show that residues may peak anywhere between 14 and 60 days after treatment, followed by a rapid decline. Residues in the leaves may be 2-10 times the level in the stalks. The increased potential for aldicarb residues in meat and milk from additional animal feed items considered by this Meeting, especially maize fodder/forage, indicates a possible need for a higher limit for carcase meat and milk. For this reason, feeding trials at feeding levels higher than 5 mg/kg in the diet are desirable. Processing studies indicate concentration of aldicarb residues only in grape pomace, raisin trash and maize hulls when grapes, sugarcane, maize and sorghum with field incurred residues were processed into their various products. However, data were inadequate for firm conclusions on residue concentration in processed products of maize, sorghum, and sugarcane. Additional studies from processing of raw commodities with higher field incurred residues are desirable for maize and sorghum. Analytical methodologies for supervised trials considered by the Meeting are basically the same as those previously considered. The Meeting did re-examine the limit of determination for the analytical method for aldicarb residues in milk. Since it was re-submitted as a result of actions of the CCPR. The Meeting considered validations conducted by the manufacturer and one government and re-affirmed 0.002 mg/kg as a reasonable level at or about the limit of determination under normal circumstances. While the Meeting recognizes that this level may not always be easily attainable under the demands of some regulatory situations, residues in milk from good agricultural practice have not been shown to exceed this level. For these reasons the Meeting cannot justify recommending a higher limit. RECOMMENDATIONS The Meeting examined residue data from supervised trials reflecting current and proposed good agricultural practices for aldicarb on a number of crops. From these data the Meeting was able to estimate additional maximum residue levels that are likely to occur when aldicarb is used in accordance with these practices and when the reported intervals from last application to harvest are observed. Residues refer to aldicarb, aldicarb sulphoxide, and aldicarb sulphone expressed as aldicarb. Maximum Interval Between Commodity Residue Level last application (mg/kg) and harvest (days) Maize (grain) 0.05 80 Maize (forage) 20 (dry weight basis) Maize fodder 2 (dry weight basis) 80 Pecans 0.5 Sorghum (grain) 0.2 90 Sorghum fodder 0.5 (dry weight basis) application at planting Sweet potatoes 0.1 120 FURTHER WORK OR INFORMATION Desirable 1. Additional good agricultural practice information, especially for maize, sorghum and grapes. 2. Additional supervised field trials data for grapes (closely following approved practice). 3. Additional processing studies for maize and sorghum, with field incurred residues at sufficiently high levels to allow a more conclusive estimate of residues in the various processed fractions. 4. Feeding studies in cattle at levels greater than 5 mg/kg in the diet. 5. Selected studies on lemons (and ideally also on Valencia oranges) in which aldicarb is applied in accordance with good agricultural practice at maximum recommended rates and harvested at approximately 30 days after treatment. Study details should be recorded, including amount and frequency of precipitation or irrigation. REFERENCES Dourough, H.W., Davis, R.B. and Ivie, G.W. Fate of Temik - Carbon-14 1970 in lactating cows during a 14-day feeding period. Journal of Agricultural Food Chem. 18: 135-142. CIVO. Information provided by the Netherlands government. 1981 CIVO. Information provided by the Netherlands government. 1982 Hicks, W., Dourough, H.W. and Mehendele, H.M. Metabolism of aldicarb 1972 pesticide in laying hens, Journal of Agricultural Food Chem. 20: (I): 151-156. Lykins, H.F. Temik pesticide. The determination of Temik sulphoxide 1969 and temik sulphone in milk. Project No. 111A13, 22 May 1969. Report submitted to the 1982 JMPR by Union Carbide, July 1982. (Unpublished) Romine, R.R. Aldicarb pesticide. Aldicarb residues in milk and meat of 1973 cows fed aldicarb aldicarb sulphoxide and aldicarb sulphone in the daily diet. Project no. 111A13, 27 February 1973. (Unpublished) Romine, R.R. Aldicarb residues in products from dry milling of 1981 Temik(R)-treated corn, Project No. 813C50, 15 October 1981. Report submitted by Union Carbide. (Unpublished) Smith, F.F. Report of residue analysis, PCY-G8-11. Report submitted by 1968 Union Carbide. (Unpublished) Union Carbide. Grapes, maize, maize fodder, tomatoes. Submission to 1982a the 1982 JMPR by Union Carbide Agricultural Products Co., Inc. (Unpublished) Union Carbide. Summary aldicarb residue data. 1982b Union Carbide. Residues of aldicarb in food and their evaluation; 1982c pecans, sorghum, sorghum fodder, sugarcane and sweet potatoes. Report submitted to the 1982 JMPR by Union Carbide. (Unpublished) Union Carbide. Pecans, sorghum, sorghum fodder, sugarcane, sweet 1982d potatoes, grapes, maize, maize fodder and tomatoes. Report submitted to the 1982 JMPR by Union Carbide. (Unpublished) Union Carbide. Aldicarb residue data sheets for potatoes. Submitted 1982e to 1982 JMPR by Union Carbide. (Unpublished) Union Carbide. Introduction to citrus fruits and potatoes, July 1982f 1982. Document submitted to the 1982 JMPR by Union Carbide. (Unpublished) Union Carbide. Aldicarb residue data for tomatoes, October, 1982. 1982g Data submitted by Union Carbide. (Unpublished) Union Carbide. Aldicarb residue data on citrus. Report submitted by 1982h Union Carbide. (Unpublished)
See Also: Toxicological Abbreviations Aldicarb (EHC 121, 1991) Aldicarb (HSG 64, 1991) Aldicarb (ICSC) Aldicarb (Pesticide residues in food: 1979 evaluations) Aldicarb (Pesticide residues in food: 1992 evaluations Part II Toxicology) Aldicarb (IARC Summary & Evaluation, Volume 53, 1991)