title: Surface-catalyzed transformations of aqueous endosulfan.
abstract: We report the effect of suspended solids on the oxidation and hydrolysis of the insecticide endosulfan (alpha and beta isomers) and its degradation products: endosulfan diol, endosulfan sulfate, endosulfan ether, and endosulfan lactone in 0.001 M NaHCO3 buffer (pH 8.15). Suspensions of sea sand, TiO2, alpha-Fe2O3, alpha-FeOOH, Laponite, and SiO2 all catalyzed the hydrolysis of endosulfan to the less toxic endosulfan diol. Suspended creek sediment (Bread and Butter Creek SC, 4% OC) inhibited endosulfan hydrolysis. Heterogeneous and homogeneous rate constants of endosulfan hydrolysis were measured and indicate that beta-endosulfan hydrolyzes faster than alpha-endosulfan. This observation was explained by a more stable transition state for beta-endosulfan that was confirmed with ab initio molecular orbital calculations (STO-6G) on the anionic intermediates of endosulfan hydrolysis. Rates of endosulfan hydrolysis over the different surfaces corresponded to their tritium-exchange site-density and suggest a mechanism involving surface coordination prior to nucleophilic attack. The oxidation of alpha-endosulfan and beta-endosulfan to the persistent pollutant endosulfan sulfate was not observed in this study.
authors.affiliation: Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, USA.
authors.forename: Spencer S
authors.initials: SS
authors.lastname: Walse
authors.forename: Ken D
authors.initials: KD
authors.lastname: Shimizu
authors.forename: John L
authors.initials: JL
authors.lastname: Ferry
mesh_terms: D002384:Catalysis; D004726:Endosulfan / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry; D006843:Hydrocarbons, Chlorinated; D006868:Hydrolysis; D007306:Insecticides / Q000737:chemistry*; D007700:Kinetics; D010084:Oxidation-Reduction; D012989:Soil Pollutants / Q000032:analysis
chemical_list: D006843:Hydrocarbons, Chlorinated; D007306:Insecticides; D012989:Soil Pollutants; D004726:Endosulfan