Transformation of two chlorinated fumigants by hydrogen sulfide species

AGRO 7

Wei Zheng, wzheng@ussl.ars.usda.gov, Department of Environmental Sciences, University of California Riverside, Riverside, CA 92521 and Scott R. Yates, Syates@ussl.ars.usda.gov, U.S. Salinity Laboratory, USDA-ARS, 450 W. Big Springs Road, Riverside, CA 92507.
The chlorinated fumigants chloropicrin and 1,3-dichloropropene (1,3-D) are extensively used to control soilborne pests. Transformation of these two pesticides by hydrogen sulfide species (H2S and HS-) was examined in well-defined anoxic aqueous solutions. Chloropicrin underwent an extremely rapid redox reaction in the hydrogen sulfide solution. Transformation products indicated reductive dechlorination of chloropicrin by hydrogen sulfide species to produce dichloro- and chloronitromethane. For 1,3-D, kinetics and transformation products analysis revealed that the reaction between 1,3-D and hydrogen sulfide species is an SN2 nucleophilic substitution process, in which the chlorine at C3 of 1,3-D is substituted by the sulfur nucleophile to form corresponding mercaptans. The transformation of chloropicrin and 1,3-D in hydrogen sulfide solution significantly increased with increasing pH, suggesting that the reactivity of hydrogen sulfide species stems primarily from HS-. Because of the relatively low smell threshold values and potential persistence of organic sulfur products, the environmental behaviors of transformation products of 1,3-D and HS- need be assessed.