Insights into reductive dechlorination of triclocarban in river sediments: Field measurements and in vitro mechanism investigations

Triclocarban (TCC) reductive dechlorination was investigated using a combination of field and laboratory experiments. Field monitoring revealed that TCC reductive dechlorination in river sediments leads to formation of two isomers of its lesser chlorinated congener namely 3,4'-dichlorocarbanilide and 4,4'-dichlorocarbanilide. Monochlorocarbanilide was not detected in sediments supporting that transformation of dichlorocarbanilide into monochlorocarbanilide is the rate limiting step of TCC dechlorination. In vitro experiments were conducted to study TCC potential reductive dechlorination mechanisms. These experiments demonstrated that 4,4'-dichlorocarbanilide was specifically formed upon a nucleophilic addition reaction under anaerobic conditions. The 3,4'-diclorocarbanilide was formed upon a two steps radical mechanism under aerobic conditions which includes TCC activation by one electron oxidation followed by a nucleophilic substitution reaction with glutathione. In vitro results suggested that strict anaerobic conditions might not be required for TCC reductive dechlorination in the environment. Moreover, in vitro reactions were performed using biomimetic or enzymatic systems supposing that TCC dechlorination might occur through microbial action in situ. Measured dichlorocarbanilide isomers/triclocarban ratios were used to evaluate the relative significance of both dechlorination pathways and the pathway leading to 3,4'-dichlorocarbanilide was found significant in all investigated river sediment samples. (C) 2015 Elsevier Ltd. All rights reserved.