Chloroform
(CF) is a widely used chemical reagent and disinfectant
and a probable human carcinogen. The extensive literature on halocarbon
reduction with zerovalent iron (ZVI) shows that transformation of
CF is slow, even with nano, bimetallic, sulfidated, and other modified
forms of ZVI. In this study, an alternative method of ZVI modificationinvolving
simultaneous sulfidation and nitridation through mechanochemical ball
millingwas developed and shown to give improved degradation
of CF (i.e., higher degradation rate and inhibited H2 evolution
reaction). The composite material (denoted as S–N(C)–ZVI)
gave synergistic effects of nitridation and sulfidation on CF degradation.
A complete chemical reaction network (CRN) analysis of CF degradation
suggests that O-nucleophile-mediated transformation pathways may be
the main route for the formation of the terminal nonchlorinated products
(formate, CO, and glycolic polymers) that have been used to explain
the undetected products needed for mass balance. Material characterizations
of the ZVI recovered after batch experiments showed that sulfidation
and nitridation promoted the formation of Fe3O4 on the S–N(C)–ZVI particles, and the effect of aging
on CF degradation rates was minor for S–N(C)–ZVI. The
synergistic benefits of sulfidation and nitridation on CF degradation
were also observed in experiments performed with groundwater.