Reaction of chlorpyrifos-methyl in aqueous hydrogen sulfide/bisulfide solutions

The kinetics of the reactions of chlorpyrifos-methyl, an organophosphorus insecticide, with hydrogen sulfide (H(2)S) and bisulfide (HS(-)) were determined in well-defined aqueous solutions. The resulting pseudo-first-order rate constant for chlorpyrifos-methyl with bisulfide yielded a second-order rate constant of (2.1 +/- 0.3) x 10(-3) M(-1) s(-1). The second-order rate constant for chlorpyrifos-methyl with hydrogen sulfide is significantly slower than the second-order rate constant with bisulfide. The contribution of H(2)S to the observed degradation rate constant of chlorpyrifos-methyl at concentrations of up to 4 mM H(2)S is not significant. The second-order rate constant of chlorpyrifos-methyl with H(2)S was too low to be measured in this study. The results indicate that HS(-) present at environmentally relevant concentrations may represent an important sink for phosphorothionate triesters in a coastal marine environment, while H(2)S reacts too slowly to be environmentally relevant (pH 6-9). Trichloropyridinol, the major product of hydrolysis of chlorpyrifos-methyl, is only a minor product of the reaction of chlorpyrifos-methyl with bisulfide; however, trichloropyridinol was found to be stable under the experimental conditions.