Methomyl

Synonyms 1 -(methylthio)ethylideneamino methylcarbamate thio-A- ((methylearba-moy)oxy)acetimidie acid methyl ester 1 - (methylthio)acetaldehyde- O-methyIcar-bamoyl oxime methylacetimidothioic acid iV-(methylcarbamoyl) ester methyl N-((methylcarbamoyl)oxy)thioacetimidate Lannate Mesomule DuPont 1179. 

White crystalline solid with slight sulfurous odor melts at 78°C (172.4°F) vapor pressure 

Extremely toxic by oral route moderately toxic by inhalation exhibits acute, delayed, and chronic effects cholinesterase inhibitor symptoms are those of phosphate — or carbamate esters—the major signs of which are increased salivation, lacrimation, spontaneous urination, blurred vision, pinpoint pupils, tremor, twitching of muscle and loss of coordination confusion, convulsions, and coma may occur as well other signs of poisoning include nausea, vomiting, cramps, diarrhea, slow heart rate, shortness of breath, and pulmonary edema (U.S. ERA 1988) death may result from respiratory arrest (Gosselin et al. 1984) the probable lethal dose from ingestion in adult human could be 

5-2 g oral lethal dose in dog 30 mg/kg, and monkey 40 mg/kg toxic effects from skin absorption low listed as extremely hazardous substance by the U.S. EPA. 

LD50 oral (mouse) 10 mg/kg LD50 oral (rat) 17 mg/kg LD50 inhalation (rat) 77 ppm 

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Environmental. The A/-methylcarbamates generally are biodegradable and of low soil persistence with half-Hves for carbaryl and aldicarb of 1—2 weeks and of carbofuran of 1—4 months. Certain carbamates are highly toxic to birds with oral LD qS for mallard, eg, pheasant, in mg/kg carbofuran, 0.40, 4.2 mexacarbate, 3.0, 4.5 and methomyl, 16, 15 compared to carbaryl >2000. Fish toxicity of carbamates is generally low, but these compounds are extremely toxic to bees. In cases of human poisoning, atropine is a specific antidote. 

PHOTOCHEMICAL BEHAVIOR OF THE INSECTICIDE METHOMYL IN ORGANIC SOLVENTS... 

Insecticide methomyl is a very toxic pesticide and is highly soluble in water (57.9 g/1). It has a low sorption affinity to soil and can cause groundwater and surface water contamination in agricultural areas. Solubilities of methomyl in different solvents are in methanol 1000 g/1, in aceton 730 g/1, in ethanol 420 g/1, in isopropanol 220 g/1, in toluene 30 g/1. 

This study describes the direct photochemical degradation of the methomyl presents at low concentration in different ogranic solvents. Also the kinetic behavior of photolytic reaction of methomyl with solvents has been studied. 

Under the conditions it was found that the methomyl was effectively decomposed in different organic solvents and reaction s rate dependes on type of solvents. 

Figure 13.15 Chromatograms obtained by on-line ti ace enrichment of 50 ml of Ebro river water with and without the addition of different volumes of 10% Na2S03 solution for every 100 ml of sample (a) blank with the addition of 1000 p.1 of sulfite (b) spiked with 4 p.g 1 of the analytes and 1000 p.1 of sulfite (c) spiked with 4 p.g 1 of the analytes and 500 p.1 of sulfite (d) spiked with 4 p.g 1 of the analytes without sulfite. Peak identification is as follows 1, oxamyl 2, methomyl 3, phenol 4, 4-niti ophenol 5, 2,4-dinitrophenol 6, 2-chlorophenol 7, bentazone 8, simazine 9, MCPA 10, atrazine. Reprinted from Journal of Chromatography, A 803, N. Masque et ai, New chemically modified polymeric resin for solid-phase extraction of pesticides and phenolic compounds from water , pp. 147-155, copyright 1998, with permission from Elsevier Science.

Hepatic Effects. Normal serum liver function tests (unspecified) were observed in a 35-year-old agricultural pilot approximately 8 hours after a 45-minute dermal exposure (with presumed concurrent inhalation exposure) when his clothing became soaked in endosulfan and methomyl (Cable and Doherty 1999). 

Serum endosulfan was 4 pg/L at 30 hours after an agricultural pilot was exposed dermally (and probably also by inhalation) for approximately 45 minutes in clothing that was heavily contaminated with endosulfan and methomyl (Cable and Doherty 1999) the dermal exposure level was not estimated and no other measures of tissue levels of endosulfan were obtained. A study by Kazen et al. (1974) has identified endosulfan residues on the hands of workers after relatively long periods free from exposure. Endosulfan residues were identified on the hands of one worker approximately 30 days after exposure and on the hands of one worker who had not used endosulfan during the preceding season. 

Oxime carbamates are not directly amenable to gas chromatography (GC) because of their high thermal instability, which often leads to their breakdown at the injection port or in the column during analysis. Analysis of oxime carbamates by GC with sulfur detection or flame photometric detection involves oxidation of the intact insecticides or alkaline hydrolysis to form the more volatile but stable oxime compound. Enzymatic techniques have been reported for the analysis of these compounds. Enzyme-linked immunosorbent assay (ELISA) has been used to determine aldicarb and its sulfone and sulfoxide metabolites and methomyl in water, soil, and sediment samples. 

The post-column reactions of methomyl are illustrated in Equations (1) and (2). 

Table 2 HPLC/fluorescence analysis of methomyl in crops (Multi-residue Method 2)...

Oxime carbamates are generally applied either directly to the tilled soil or sprayed on crops. One of the advantages of oxime carbamates is their short persistence on plants. They are readily degraded into their metabolites shortly after application. However, some of these metabolites have insecticidal properties even more potent than those of the parent compound. For example, the oxidative product of aldicarb is aldicarb sulfoxide, which is observed to be 10-20 times more active as a cholinesterase inhibitor than aldicarb. Other oxime carbamates (e.g., methomyl) have degradates which show no insecticidal activity, have low to negligible ecotoxicity and mammalian toxicity relative to the parent, and are normally nondetectable in crops. Therefore, the residue definition may include the parent oxime carbamate (e.g., methomyl) or parent and metabolites (e.g., aldicarb and its sulfoxide and sulfone metabolites). The tolerance or maximum residue limit (MRL) of pesticides on any food commodity is based on the highest residue concentration detected on mature crops at harvest or the LOQ of the method submitted for enforcement purposes if no detectable residues are found. For example, the tolerances of methomyl in US food commodities range from 0.1 to 6 mg kg for food items and up to 40 mg kg for feed items. ... 

Crops, food, and feed. The first recommended method is based on the Dutch Multiresidue Method 2 for A-methylcarbamates, which was originally developed by de Kok et The method has recently been validated by DuPont Crop Protection and Batelle, Geneva Research Centres, for the analysis of methomyl and oxamyl in dry, high-water, high-fat, and high-acid content crops and in various grape processed products. The limit of detection for each analyte is 0.003-0.005 mg kg . ... 

The first recommended soil method for oxime carbamates is the method of Honing et al. by HPLC/MS. The LOQ of the method, specifically for aldicarb, methomyl, and oxamyl, is 0.05mgkg. Soil (lOg) is Soxhlet extracted for 16h with acetone-dichloromethane (1 1) using double-thickness cellulose extraction thimbles (80 X 22-mm i.d.). Prior to extraction, the Soxhlet system and the thimbles are cleaned for 14 h by refluxing with methanol. The extracts are removed and concentrated nearly to dryness in a rotary evaporator operating at 35 °C evaporation to dryness... 

C <4.7x10 Pa at 20 °C Water 20 mg at 20 °C Readily soluble in polar organic solvents Stable in neutral and weakly basic conditions Unstable in strongly acidic or basic conditions Stable in most of organic solvents such as acetone, acetonitrile and carbon tetrachloride Undergoes hydrolysis to yield methomyl oxime in alkaline solutions... 

The residue definition includes alanycarb and its metabolite, methomyl (determined as methomyl oxime)... 

Quantitation is performed by the calibration technique. Construct a new calibration curve with methomyl oxime standard solutions (0.2, 0.4, 0.6, 0.8 and 1.0 xgmL in acetone) for each set of analyses. Plot the peak area against the injected amount of methomyl oxime on logarithmic paper. As the amount of alanycarb is measured in terms of its oxime derivative, a conversion factor of 3.8 (the molecular weight ratio of alanycarb to methomyl oxime) should be applied to obtain the net amount. The injection volume should be kept constant as the peak area varies with the injection volume in flame photometric detection. Before each set of measurements, check the GC system by injecting more than one standard solution containing ca 2-10 ng of methomyl oxime. 

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