BENOMYL JMPR 1973 IDENTITY Chemical names Methyl 1-(butylcarbamoyl)benzimidazol-2-ylcarbamate Methyl 1-(butylcarbamoyl)-2-benzimidazole carbamate 1-(butylcarbamoyl)-2-benzimidazole carbamic acid methyl ester Synonyms Benlate (R), Du Pont Fungicide 1991 Structural formulaOther information on identity and properties Molecular weight: 290.3 State: White crystalline solid Melting point: Decomposition before melting Solubility: Water: practically insoluble Oil: practically insoluble Chloroform: 9.4 g/100 ml Dimethylformamide: 5.3 g/100 ml Acetone: 1.8 g/100 ml Xylene: 1.0 g/100 ml Ethanol: 0.4 g/100 ml Heptane: 0.04 g/100 ml Purity: Technical benomyl better than 98% (w/w) Chemical stability: Benomyl is easily hydrolyzed to (see Fig. 1) methyl 2-benzimidazole carbamate (MBC) in very dilute aqueous, and in acidified methanolic solutions. MBC in turn hydrolyzes under basic conditions to give 2-aminobenzimidazole (2-AB) By direct alkaline treatment of benomyl a triazine ring-closure takes place, forming 3-butyl-S-triazino [1.2 a] benzimidazole-2.4(1H, 3H)dione (STB) which is not stable in hot alkali. It is further converted to the stable 2-(3-butylureido)-benzimidazole (BUB) (Ogawa et al., 1971; White et al., 1973). By exclusion of moisture formulated benomyl products are stable. Use pattern Benomyl is, since 1970, registered as a systemic fungicide in a great number of countries, including the United States of America. It is marketed mostly as a 50% wettable powder. Similar to other benzimidazole fungicides it is active against a broad spectrum of fungi, among which are Ascomycetes, Basidiomycetes and some Deuteromycetes, while it is found completely inactive against the Phycomycetes fungi (Edgington et al., 1971; Bollen, 1972). Among the well-controlled fungal diseases are powdery mildew, apple scab (Venturia inaequalis) and the grey mould fungus Botrytis cinerea (Evans, 1971). The major uses of benomyl for the control of fungal diseases on fruits, vegetables and ornamenthals are preharvest applications which usually involve one or more sprayings with from about 20 g to about 20 g a.i. per 100 litres (Table 1). Post-harvest treatments, by either dipping or dusting, within the same concentration range are approved for the protection of fruits, seeds and vegetables in storage. The United States Environmental Protection Agency has registered post-harvest uses of benomyl for apricots, cherries, citrus, nectarines, peaches, plums and prunes. Residues resulting from supervised trials The levels of benomyl residues found in various crops in the United States of America and other countries are summarized in Table 1 (Anonymous, 1972, 1973). The data are based on information supplied to the United States Environmental Protection Agency to support the establishment of United States tolerances, indicating the residues resulting from approved use patterns, Residue levels are given as the range of values observed in those crops showing benomyl residues (incl. MBC).
TABLE 1. RESIDUES OF BENOMYL IN VARIOUS CROPS (Supervised trials) Application Benomyl Crop Rate No. per residue (approx.) season founda range (ppm) Apricots 0.3-0.6 g/l 2-3 2.6-6.5 Dip post-harvest 0.9-5.1 Almonds nutmeats 1-2 kg/ha 1-3 <0.1 hulls 1-2 kg/ha 1-3 0.2-0.74 Apples 0.4-1.2 g/l 6-12 0.5-4.8 Dip post - harvest 0.12-0.88 Avocados 1-2 kg/ha 3-6 0.11-0.18 Bananas 0.2-0.3 kg/ha 6-9 Pulp <0.1 0.3-0.6 g/l Dip 0.15-0.43 post-harvest Barley 0.5 kg/ha 2 Straw 0.54 1.53 (53 days) Grain 0.1 Beans dry 1.5-2 kg/ha 2-3 0.1-0.73 lim 1.5-2 kg/ha 2-3 0.5-1.8 snap 1.5-2 kg/ha 1-2 0.11-0.94 Bean vines 1.5-2 g/ha 2-3 0.2-4.6 Blackcurrant 0.45 kg/ha 1 4.0-5.1 (0 day) 1.7-2.4 (7 day) 1.3-2.4 (14 day) Caneberries 0.5-2 kg/ha 2-5 0.75-6.0 Celery 0.2-0.5 kg/ha 4-11 0.1-2.6 TABLE 1. (Cont'd.) Application Benomyl Crop Rate No. per residue (approx.) season founda range (ppm) Cherries 0.3-0.6 g/l 2-3 0.2-12.6 0.3 g/l Dip 0.5-2.3 post-harvest Citrus (whole 0.6-1.1 g/l 1-5 0.2-1.3 fruit) 500 ppm Dip 0.54-1.26 post-harvest 1000 ppm Dip 0.39-2.35 post-harvest 1250 ppm Dip 1.3-1.8 post-harvest 2500 ppm Dip 2.7-3.9 post-harvest 5000 ppm Dip 4.5-5.4 post-harvest Cucumbers 0.2-0.5 kg/ha 2-6 0.13-0.55 Grapes 1-1.5 kg/ha 3-5 0.14-10.3 Macadamia nuts 2-2.5 kg/ha 4-10 <0.1 Mangoes 1-2 kg/ha 5-17 0.15-3.0 Melons 0.2-0.4 kg/ha 2-7 0.27-0.32 Mushroom 0.25 g/m2 1 0.31-0.57 0.5 g/m2 (peat treatment) 1 0.23-0.51 1.0 g/m2 (peat treatment) 1 0.88-1.5 Nectarines 0.5 kg/ha 1-3 1.6-2.2 Peaches 0.2-0.6 g/l 1-15 0.2-8.2 0.3 g/l Dip 3.9-4.7 post-harvest Peanuts 0.2-0.5 kg/ha 2-13 <0.1 Peanuts hay 0.4-1 kg/ha 3-13 1.4-1.6 TABLE 1. (Cont'd.) Application Benomyl Crop Rate No. per residue (approx.) season founda range (ppm) Pears 0.6-1.2 g/l 3-5 1.7-3.2 Dip post-harvest 0.1-0.55 Pecans 1-1.25 kg/ha 3-6 <0.1 Prunes, plums 0.3-0.6 g/l 2-4 0.4-1.4 0.3 g/l Dip 0.5-1.9 post-harvest Potato 50 g/100 kg Tuber <0.1 dressing Squash 0.4-0.8 kg/ha 2-5 0.10-0.50 Strawberries 0.3-0.6 g/l 3-7 0.43-2.6 0.3-0.6 g/l 6-7 2.7-15.2 (Under glass) (0.day) 0.3-0.6 g/l (Under glass) 1.5-2.6 (17.day) Sugarbeet roots 0.2-0.5 kg/ha 3-6 <0.1 tops 0.4-1 kg/ha 1-6 0.15-4.7 Tomato 0.3 g/plant 1 1.1-2.2 0.3-0.7 kg/ha 3 0.15-2.1 (Under glass) Application Benomyl a Total residue comprising benomyl, methyl benzimidazolecarbamate and 2-aminobenzimidazole, expressed as benomyl. (Nominal blank values either 0.1 or 0.2 ppm, apart from citrus, strawberries, peanut hay, barley straw and lettuce (0.3-0.4 ppm).) Fate of residues General remarks on mode of action As suggested by Clemons and Sisler (1969) (Kilgore and White, 1970; Helweg, 1973) and others, it is generally accepted that methyl 2-benzimidazole carbamate (MBC), which is the major metabolite of benomyl, is primarily responsible for the fungitoxicity of the latter. Comparisons between the effects of benomyl and MBC (Hammerschlag and Sisler, 1973) indicated that both compounds caused an inhibition in the synthesis of DNA, but that this was secondary to a mitotic arrest of fungal cell division, followed by an inhibition of cytokinesis. Benomyl partially inhibits respiration of subcellular particles from fungal cells, while MBC had essentially no such effect. This differential effect of benomyl and MBC on metabolism is attributed to the formation, from benomyl, of volatile butyl isocyanate (BIC), simultaneously to MBC production. Fungitoxicity of benomyl preparations may thus be attributed to the combined effects of its two first breakdown products, MBC and BIC. Although the fungitoxic effects of benomyl are thus assumed to be caused by its metabolites, MBC and BIC, much of its systemic functions may be connected to benomyl per se. Controlled experiments of foliar treatments on apples, cucumber, banana, orange and grape plants indicate that from 48% to 77% of the 14C-benomyl remaining 21-23 days after application under outdoor conditions was still in the form of intact benomyl (Baude et al., 1973). Several workers have recently found that plant penetration and movement through the cuticle after foliar application is greater for benomyl than for MBC (Upham and Delp, 1973; Hammerschlag and Sisler, 1972, 1973; Solel and Edgington, 1973). Systemic translocation within the plant, on the other hand, is mostly in the form of MBC plus smaller amounts of 2-AB (Siegel and Zabbia, 1972). The two theoretical metabolites, STB and BUB (see Fig. 1), which are formed chemically under alkaline conditions could not be detected by Baude et al. (1973) as actual conversion products from benomyl under greenhouse conditions or in field tests, even when subjected to the influence of two alkaline pesticides, basic copper sulfate and lime sulfur. Plants Under practical conditions a considerable part of the applied benomyl is claimed to remain on the foliar surfaces, as relatively stable residues, only gradually degrading to form MBC (Baude et al., 1973). Studies of the systemic uptake of benomyl after foliar treatments indicate that while the total amount which penetrates the surface is relatively small, residues can still be traced in untreated portions of the plant (Lowen, 1973). The translocated residues consist mainly of MBC together with smaller amounts of 2-AB. To the plants these compounds move only passively, i.e. they are carried by the intercellular transpiration stream towards the edges and tips of leaves (Foldo, 1973), where they then accumulate. Benomyl is readily absorbed through the root-system of plants. The uptake in vegetable crops, such as lettuce and cucumber is clearly demonstrated through greenhouse trials (see Table 2) in which normal and excessive rates were applied through watering or through admixing benomyl with the soil (Green-Lauridsen and Voldum-Clausen, 1973). Citrus The total 14C-benomyl residue (benomyl + MBC) was found to decrease slowly in oranges during two months storage after post-harvest dipping. While the major part of the residue remained in the peel, a smaller, but significant amount gradually penetrated into the edible portion (see Table 3). Two weeks after the dipping 61% of the surface residue was present as unchanged benomyl, the remaining 39% being MBC (Lowen, 1973). Grapes and wine Lemperle et al. (1973) found that benomyl residues, as well as other benzimidazole fungicides, are transferred almost quantitatively into unclarified musts during wine production. During clarification and fermentation a small amount may disappear but a considerable part of the benomyl residue present in grapes may be found in wine. Animals and animal products Benomyl is readily hydrolyzed into MBC through cleavage of the 1-butyl carbamoyl side chain when ingested by mice, rabbits and sheep (Douch, 1973). Further hydrolysis of the carbamate ester bond was shown by these studies to yield 2-AB suggesting that benomyl may not remain in the unchanged form more than momentarily when residues are ingested into the alimentary tract of animals. Hydroxylated derivatives of MBC and 2-AB were identified by these studies in urine and faeces of all three species. After feeding rats with benomyl Gardiner et al, (1968) identified methyl 5-hydroxy-2-benzimidazole carbamate as the major metabolite which was liberated in urine by enzyme hydrolysis of glucuronide and/or sulfate conjugates. MBC is assumed to be the possible intermediate metabolite for this conversion as well as for the formation of a minor isomeric metabolite, methyl 4-hydroxy-2-benzimidazole carbamate, which was found in milk and meat in later studies (Gardiner et al., 1972) when feeding cows with rations containing 2, 10 and 50 ppm benomyl for 32 days (see Table 4). Neither intact benomyl nor MBC was detected in these studies. TABLE 2. BENOMYL RESIDUES ABSORBED THROUGH THE ROOTS UNDER GREENHOUSE CONDITIONS Sampling after Sampling after Treatment Application 0-14 days 15-23 days Remarks rate Range Average Range Average Summer lettuce Watering 1.5-3.8 g/10 m2 5.21-17.8 11.3 n.d.-3.09 1.38 Practical use rate Watering 7.5-15 g/10 m2 4.33-39.7 15.8 0.49-5.01 2.63 Excessive rates Watering 22.5 g/10 m2 17.7-29.3 23.0 Winter lettuce Watering 1.5-3.8 g/10 m2 11.7-18.6 15.3 7.08-14.7 10.5 Practical use rate Watering 7.5-15 g/10 m2 20.4-60.6 36.8 6.74-27.1 15.9 Excessive rates Watering 22.5 g/10 m2 56.5-97.1 74.5 28.2-32.1 30.2 Cucumber Watering 1 g/plant n.d.-0.64 0.27 0.15-0.53 0.37 Soil treatmenta 1 g/plant 0.53-2.02 1.10b a Composite Soil: 1/3 soil, 1/3 fertilizer, 1/3 peat mulch. b Sampling after 34-55 days. TABLE 3. 14C-BENOMYL RESIDUES ON ORANGES FOLLOWING POST-HARVEST DIPPING (From Lowen, 1973) ppm benomyl Days Whole in dip post-treatment Peel Pulp fruit (calculated) Untreated - <0.05 <0.05 <0.05 100 0 0.80 <0.05 0.30 31 0.46 <0.05 0.16 62 0.54 <0.05 0.19 500 0 1.5 0.08 0.46 31 1.4 0.12 0.38 62 1.6 0.17 0.50 1 000 0 5.6 <0.05 1.3 31 4.4 0.11 0.95 62 3.0 0.40 0.93 After withdrawing the treated diet for one or two days the residues of 5-hydroxy-MBC and 4-hydroxy-MBC in milk dropped to below 0.01 ppm. Water Benomyl rapidly breaks down on contact with water to give MBC, conversion being complete within four days (Kilgore and White, 1970; Peterson and Edgington, 1969). Soil Helweg (1973) isolated from soils four strains of bacteria and two fungi which promoted the breakdown of benomyl to nonfungistatic compounds. High humus content increased the rate of breakdown of benomyl. Generally, however, it was concluded that benomyl is relatively stable as a soil residue under temperate climatic conditions. TABLE 4. RESIDUES (PPM) OF METHYL 5-HYDROXY-2-BENZIMIDAZOLECARBAMATE (5-HYDROXY MBC) AND METHYL 4-HYDROXY-2-BENZIMIDAZOLECARBAMATE (4-HYDROXY MBC) FOUND IN MEAT AND MILK AFTER FEEDING COWS RATIONS CONTAINING 2, 10, AND 50 PPM BENOMYL FOR 32 DAYS (From Gardiner et al., 1972) Feeding level 2 ppm 10 ppm 50 ppm Sample 5- 4- 5- 4- 5- 4- hydroxy hydroxy hydroxy hydroxy hydroxy hydroxy MBC MBC MBC MBC MBC MBC Milk <0.01 <0.01 0.01 <0.01 0.05 0.03 Meata <0.05 <0.05 <0.05 <0.05 <0.05 <0.05 a "Meat" represents liver, kidney, fat and muscle. Studies over two years in experimental fields in Delaware, North Carolina and Florida (Baude, 1972) showed that the amount of non-volatile decomposition products of 14C-benomyl remaining in the soil after one year were 57%, 49% and 57%, respectively, of the quantity originally applied. After two years in soil in Florida, 27% of the amount originally present remained. After one month only minor amounts of unchanged benomyl were present, the principal metabolite being MBC, with smaller amounts of 2-AB. Uptake by crops grown in treated soils was studied in the same experiments by Rhodes (1972) using 14C-benomyl. Trace amounts, ranging from 0.02 to 0.08 ppm, could be found in tissues of carrots, tomatoes, corn and beans, while edible snap beans, corn and tomatoes contained less than the detection limit (i.e. <0.01 ppm). In this study the benomyl content of the soil at the time of harvest was 0.9 ppm. Methods of residue analysis Pease and Gardiner (1969) describe colorimetric and fluorometric procedures for determining benomyl in a variety of plant and animal tissues and in soil. The residue is extracted, purified by partition, converted to 2-aminobenzimidazole, and determined by direct fluorometric measurement or by colorimetric analysis following bromination. The procedure thus determines benomyl, its principal degradation product methyl 2-benzimidazole carbamate, and the minor residual component 2-aminobenzimidazole as a composite value. With a sensitivity of 0.1 ppm for 50 g samples, recoveries were about 87% for both methods. Pease and Holt (1971) improved this method to make it less time-consuming and to include the analysis of citrus fruits. By using fluorometric measurement from both acidic and basic media it was possible to distinguish between benomyl residues and other benzimidazole fungicides. Peterson and Edgington (1969) report a method to determine benomyl and the hydrolysis product, MBC, using a bioautograph technique. A thin-layer plate is sprayed with a mixture of agar and Penicillium spores, and the diameter of the zone of inhibited growth above the fungitoxic spot is related to the amount of active material in the spot. The sensitivity of the method is 0.1 ppm for a 50 g sample. Somewhat similar agar plate methods have also been described by Erwin et al. (1968), Baron (1971) and Holman and Fuchs (1970). A two-dimensional TLC-technique for separation of benomyl, MBC, 2-AB and thiophanate as well as thiophanate-methyl is described by von Stryk (1972). A UV-spectrophotometric method for determining residues in grapes, must and wine has been described by Lemperle and Kerner (1971). After addition of acetone the samples are extracted with chloroform, the chloroform evaporated to dryness and the residues measured in methanol at 301.5 nm. The limit of detection reported is 0.3 ppm for 100 g samples and recoveries of 89% for grapes, 75% for must and 56% for wines. Mestres et al. (1971) used a spectrophotometric method for fruits and vegetables, measuring the hydrolysis product, MBC, at 282 nm. The limit of detection was 0.1 ppm for 25 g samples. Residues in meat and milk have been determined by the liquid chromatographic procedure of Kirkland (1973). The method detects 4-hydroxymethyl-2-benzimidazole carbamate and 5-hydroxymethyl-2-benzimidazole carbamate, which are found in animal systems, as well as benomyl and methyl-2-benzimidazole carbamate. Kirkland et al. (1973) further adapted this method for the determination of benomyl and/or MBC and 2-AB in soil and plant material. Recoveries of the three compounds were 92, 88 and 72%, respectively. The lower limit of sensitivity of the method is 0.05 ppm for each of the components. The methods based on spectrophotofluometry of 2-AB, on UV-spectophotometry of MBC and the liquid chromatographic procedure may all be adapted for regulatory purposes. National tolerances (as notified to the meeting) Country Commodity Tolerance, ppm Australia Pome fruits, stone fruits 5 Vegetables, citrus 3 Grapes, mangoes, avocados strawberries 2 Bananas 1 Peanuts 0.2 Belgium Apples, pears, cucumbers, strawberries, celery, small grain 1 Canada Peaches 15 Blackberries, boysenberries, raspberries 6 Apples, apricots, cherries, crabapples, grapes, nectarines, pears, plums, prunes, strawberries 5 Federal Citrus fruits 10 Republic Grapes 3.0 of Berries 2.0 Germany Vegetables (exc. cucumber), Total stone fruit, bananas, citrus residue fruits (without peel) 1.0 calculated Cereals, cucumbers 0.5 as benomyl Banana (without peel) 0.2 Other vegetable products 0.1 United Apricots, cherries, nectarines, States of peaches and plums (including America fresh prunes) (from post- harvest and/or pre-harvest applications), peanut hay, peanut forage, sugar beet tops 15 Mushrooms 10 Apples, pears, blackberries, boysenberries, dewberries, loganberries, raspberries 7 Strawberries 5 Celery, mango 3 Snapbeans, peanut hulls 2 National Tolerances (cont'd) Country Commodity Tolerance, ppm Bananas (whole), cucumbers, melons, summer squash, winter squash, avocado, almond hulls 1 Banana (pulp), peanuts, sugar beets (roots), nuts (almonds, Brazil nuts, bush nuts, butternuts, cashews, chestnuts, filberts, hazelnuts, hickory nuts, macadamia nuts, pecans, walnuts) 0.2 Milk and the meat, fat and meat by-products of cattle, goats, hogs, horses and sheep 0.1 Netherlands Fruit and vegetables 2 ) Determined Raw cereals 0.5 ) and Citrus fruits 3.5 ) expressed ) as ) MBC South Fruits and vegetables 3 Africa Appraisal Benomyl is a relatively new systemic broad-spectrum fungicide already established in most countries. It is marketed as wettable powders and used in foliar applications, seed treatments and post-harvest dipping procedures on a great number of food and forage crops. Benomyl is chemically easily hydrolysed into the relatively stable methyl-2-benzimidazole carbamate (MBC) which is considered to be the major fungitoxic principle of the compound. Formulated benomyl may hydrolyze if not kept dry in storage. A fungicidal effect additional to the MBC activity is claimed to be connected with the simultaneous release of volatile butyl isocyanate. Recent data has been presented suggesting that the hydrolytic breakdown is of significance for the systemic properties of benomyl facilitating the cuticular penetration. Evidence is given that in the case of benomyl residues on foliar surfaces the formation of MBC proceeds gradually. In a typical example a 50% cleavage of residues remaining on apple leaves occurs three weeks after application. A further metabolic product found in plants is 2-aminobenzimidazole formed from MBC. The amount of this metabolite found in plant material is, however, usually relatively small; so far not being found in excess of 1% of total residues. For practical purposes therefore, residues in plant material following application of benomyl could be considered as the composite of benomyl, MBC and 2-AB or as the sum of benomyl and MBC alone. Residue data justifying the establishment of several national tolerances were available to the meeting, together with limited information on residues on citrus fruits sampled from trade channels. Included also is evidence of uptake into crops from treated soils. Half-life of benomyl (metabolized to MBC) in soils varies from about four months to one year indicating relatively long persistence with a possibility of unintentional uptake by following crops. Cow feeding trials show that hydroxylated methyl benzimidazole carbamates are formed from benomyl with MBC as the probable intermediate metabolite. The most recent published report has confirmed this information indicating that MBC (and possible 2-AB) are likely to be the primary chemical entities to be absorbed from the alimentary tract following the ingestion of benomyl residues. The presence of hydroxylated MBC was demonstrated in milk and meat residues of intact benomyl or MBC were detected. Suitable methods of analysis for benomyl, MBC and 2-AB or for benomyl and MBC as composite values have been published, both methods being effective at the 0.1 ppm level. For one of these methods which is based on spectrophotofluorometric measurement, modifications have been introduced which allow the determination of benomyl and metabolites and to differentiate these from other benzimidazole fungicides such as thiabendazole. Although useful for regulatory purposes neither of the two methods, however, permits the separate determination of benomyl and metabolites when these are present together. RECOMMENDATIONS As no acceptable daily intake was established it was not possible to recommend tolerances. Following officially acceptable use in various countries residues of benomyl and its metabolites can occur in the following commodities up to levels indicated. Residues of benomyl should be measured as the composite of benomyl and its main metabolite, methyl benzimidazolecarbamate with or without minor amounts of 2-aminobenzimidazole (usually less than 1% of total residues), calculated as methyl benzimidazolecarbamate. The levels indicated are not likely to be exceeded when benomyl is applied in accordance with good agricultural practice, including either or both pre-harvest and post-harvest treatments (when applicable). These levels have been recommended as guideline levels. For the underlined commodities adjustments have been made to recommendations in order to accommodate good agricultural practices for such alternative systemic fungicides of which MBC is also recognized and identified as the major metabolite and/or chemical entity (i.e. carbendazim and thiophanatemethyl). Guideline levels ppm Citrus fruit (whole), cherries, grapes, peaches 10 Apples, pears, apricots, tomatoes, blackberries, boysenberries, dewberries, loganberries, raspberries, strawberries, blackcurrants 5 Celery, prunes, plums, beans (lima), mangoes, beans (dry), beans (snap), nectarines 2 Mushroom, banana (whole) 1 cucumbers, melons, squash, brussels sprouts, avocados 0.5 Sugar beet, raw cereals, peanuts, almonds, macadamia 0.5 Nuts, pecans, potatoes 0.1a Animal feedstuffs Bean vines 30 Sugar beet leaves 5 Peanut hay, barley straw 2 Almond hulls 1 Meat of cattle and sheep 0.1a Milk (whole) a At or about limit of determination. Residues to be measured as a composite of benomyl, MCB, 2-AB and expressed as MBC. FURTHER WORK OR INFORMATION Required (before an acceptable daily intake can be estimated) 1. Full toxicological data. Desirable 1. Further development of analytical methods to adapt them for regulatory purposes, especially to permit separate determination of benomyl and metabolites when present together. 2. Information on residues in food in commerce. 3. Information on the nature and level of residues in poultry and eggs following the feeding of benomyl residues in rations. REFERENCES Anon. Residues of benomyl in certain foods. E.I. du Pont de 1972, 1973 Nemours & Co., Delaware. Unpublished reports filed with FAO Baron, M. Determination, migration and distribution of a 1971 systemic fungicide (benomyl) in the leaves of the banana plant. Fruits, 26: 643 Baude, F. J. Disappearance of benomyl-2-14C from field soil 1972 in Delaware, North Carolina, and Florida. Paper submitted by E.I. de Pont de Nemours & Co., Delaware (Unpublished) Baude, F. J., Gardiner, J. A. and Han, J. C.-Y. Characterization 1973 of residues on plants following spray applications of benomyl. Prepublication of paper submitted to the J. Agr. Food Chem. Bollen, G, J. A comparison of the in vitro antifungal spectra 1972 of thiophanates and benomyl. Neth J. Plant. Path. 78: 55 CIVO-TNO Unpublished reports on benomyl residues from Central 1972, 1973 Institute of Food Research (CIVO-TNO) of 11 January 1972 and 9 August 1973 Clemons, G.P. and Sisler, H. D. Formation of a fungitoxic 1969 derivative from Benlate. Phytopathology, 59: 705 Douch, P. G. C. The metabolism of benomyl fungicide in animals. 1973 Xenobiotica, 3: 367 Edgington, L. V., Khew, K.L. and Barron, G.L. Fungitoxic spectrum 1971 of benzimidazole compounds. Phytopathology, 61: 42 Erwin, D. C., Mee, H. and Sims, J. J. The systemic effect of 1968 1-(butylcarbamoyl)-2-benzimidazole carbamic acid, methyl ester, on verticillium wilt of cotton. Phytopathology, 58: 528 Evans, E. Systemic fungicides in practice, Pesticide Science, 1971 2: 192 Foldo, N. E. Systemic fungicides. Effect, advantages and 1973 disadvantages (in Danish), Ugeskr. f. agronomer og hortonomer, 40: 730 Gardiner, J. A., Brantley, R. K. and Sherman, H. Isolation 1968 and identification of a metabolite of methyl 1-(butylcarbamoyl)-2-benzimidazolecarbamate in rat urine. J. Agr. Food Chem. 16: 1050 Gardiner, J. A., Kirkland, J. J., Pease, H. L., Wall, E. N. 1973 and Morales, R. Unpublished studies. Cited from Kirkland (1973) Green-Lauridsen, M. and Voldum-Clausen, K. Reports on 1973 experiments on pesticide residues Nos 285-287, 290-293, 298-300, 302, 306, 308-310 from the Danish National Food Institute and Government Plant Pathology Institute, Copenhagen (Unpublished) Hammerschlag, R. S. and Sisler, H. D. Differential action 1972 of benomyl and methyl-2-benzimidazolecarbmate (MBC) in Saccharomyces pastorianus. Pesticide Biochem. Physiol. 2: 123 Hammerschlag, R. S. and Sisler, H. D. Benomyl and methyl-2 1973 benzimidazole (MBC): biochemical, cytological and chemical aspects of toxicity to Ustilago mavdis and Saccharomyces cerevesiae; Pesticide Biochemistry and Physiology, 3: 42 Helweg, A. Persistence of benomyl in different soil types 1973a and microbial breakdown of the fungicide in soil and agar culture. Tidskr. for Planteavl (Copenhagen), 77: 232 Helweg, A. Influence of the fungicide benomyl on micro-organisms 1973b in soil. Tidsskrift for Planteavl (Copenhagen), 77: 375 Holman, A. L. and Fuchs, A. Direct bioautography on TLC as 1970 a method for detecting fungitoxic substances. J. Chromatography, 51: 327 Kilgore, W. W. and White, E.R. Decomposition of the systemic 1970 fungicide 1991 (Benlate). Bull. Environm. Contam. & Toxicol. 5: 67 Kirkland, J. 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See Also: Toxicological Abbreviations Benomyl (EHC 148, 1993) Benomyl (HSG 81, 1993) Benomyl (ICSC) Benomyl (WHO Pesticide Residues Series 5) Benomyl (Pesticide residues in food: 1983 evaluations) Benomyl (JMPR Evaluation 1995 Part II Toxicological and environmental)