title: Reduction of the carbamate pesticides oxamyl and methomyl by dissolved FeII and CuI.
abstract: The degradation of two oxime carbamate pesticides, oxamyl and methomyl, was investigated in anoxic solutions containing various metal ions and reducing agents. In reagent-free solutions, these carbamates degrade slowly via base-catalyzed elimination. Rates of carbamate degradation are accelerated by Fe(II), Cu(I), and Cu(II), but not by several other metal ions and reducing agents. In the presence of Fe(II), carbamates undergo a net two-electron reduction that is coupled to the sequential one-electron oxidation of two Fe(II) ions. The observed products are a substituted nitrile, methanethiol, and methylamine. A radical intermediate is inferred by polymerization of the radical scavenger acrylonitrile. Redox kinetics (i) vary with carbamate identity, (ii) exhibit first-order dependence on both Fe(II) and carbamate concentration, (iii) are relatively independent of pH, (iv) follow Arrhenius temperature dependence, and (v) are only indirectly influenced by the presence of O2. Coordinatively saturated Fe(II) complexes (Fe(II)EDTA2- and Fe(II)(CN)6(4-)) react with oxamyl at rates equal to and greater than hexaquo Fe(II), respectively, indicating that an inner-sphere Fe(II)-carbamate coordination complex is not required for electron transfer. Experimental results indicate that Cu(I) reduces the carbamates by the same mechanism as Fe(II) but at much higher rates. In contrast, Cu(II) acts as a catalyst for both elimination and reduction reactions.
authors: Department of Geography and Environmental Engineering, Johns Hopkins University, Baltimore, Maryland 21218, USA. strathma@jhu.edu
authors: T J
authors: TJ
authors: Strathmann
authors: A T
authors: AT
authors: Stone
mesh_terms: D002219:Carbamates / Q000737:chemistry*; D002384:Catalysis; D003300:Copper / Q000737:chemistry; D005296:Ferrous Compounds / Q000737:chemistry*; D000860:Hypoxia; D007306:Insecticides / Q000737:chemistry*; D008724:Methomyl / Q000737:chemistry*; D010084:Oxidation-Reduction; D012989:Soil Pollutants / Q000032:analysis*; D012995:Solubility
chemical_list: D002219:Carbamates; D005296:Ferrous Compounds; D007306:Insecticides; D012989:Soil Pollutants; D008724:Methomyl; D003300:Copper; C011960:oxamyl