Dehalogenation of Halogenated Fumigants by Polysulfide Salts

• Published in: Journal of agricultural and food chemistry 2006-07, Vol.54 (15), p.5503-5508
• Main Authors: Bondarenko, S, Zheng, W, Yates, S. R, Gan, J
• Format: Article
• Language: English
• Subjects: 1,3-dichloropropene; Allyl Compounds - chemistry; Biological and medical sciences; chloropicrin; dehalogenation; Drug Stability; Food industries; fumigants; Fumigation; Fundamental and applied biological sciences. Psychology; Gas Chromatography-Mass Spectrometry; Halogens - chemistry; Hydrocarbons, Chlorinated - chemistry; Hydrocarbons, Iodinated - chemistry; Kinetics; methyl iodide; Pesticides - chemistry; polysulfide salts; polysulfides; reaction kinetics; Solutions; Sulfides - chemistry
• ISSN: 0021-8561; 1520-5118
• DOI: 10.1021/jf0606914

Halogenated fumigants are among the most heavily used pesticides in agriculture. Because of their high mobility and toxicological characteristics, the contamination of air or groundwater by these compounds has been a great environmental concern. In this study, we investigated dehalogenation of several halogenated fumigants by polysulfides. The reaction of polysulfides and methyl iodide (MeI), 1,3-dichloropropene (1,3-D), and chloropicrin (CP) was very rapid. When the initial fumigant and polysulfide concentrations were both 0.2 mM, the observed 50% disappearance time values (DT50) of MeI, cis-1,3-D, and trans-1,3-D were 27.2, 29.6, and 102 h, respectively. When the initial polysulfide concentration was 1.0 mM, the corresponding DT50 values were only 2.2, 1.6, and 3.8 h. Under similar conditions, the reaction with CP was even more rapid than with the other fumigants. In 0.2 mM polysulfide solution, more than 90% of the spiked CP disappeared in 1 h after the initiation of the reaction. The reaction between fumigants and polysulfides also progressed at enhanced rates when the polysulfide solution was initially purged with nitrogen. Analysis of reaction kinetics and initial products suggests that the reaction is SN2 nucleophilic substitution for MeI and 1,3-D but likely reductive dehalogenation for CP. Given the high reactivity of polysulfide salts toward halogenated fumigants, this reaction may be used as a pollution mitigation strategy, such as for disposal of fumigant wastes, treatment of fumigant-containing wastewater, and cleanup of fumigant residues in environmental media. Keywords: Halogenated fumigants; polysulfide salts