Sulfidized nanoscale zerovalent iron (SNZVI) with desirable properties and reactivity has recently emerged as a promising groundwater remediation agent. However, little information is available on how the molecular structure of chlorinated ethenes (CEs) affects their dechlorination by SNZVI or whether the sulfur content of SNZVI can alter their dechlorination pathway and reactivity. Here, we show that the reactivity (up to 30-fold) and selectivity (up to 70-fold) improvements of SNZVI (compared to NZVI) toward CEs depended on the chlorine number, chlorine position, and sulfur content. Low CEs (i.e., vinyl chloride and cis-1,2-dichloroethene) and high CEs (perchloroethene) tended to be dechlorinated by SNZVI primarily via atomic H and direct electron transfer, respectively, while SNZVI could efficiently and selectively dechlorinate trichloroethene and trans-1,2dichloroethene via both pathways. Increasing the sulfidation degree of SNZVI suppressed its ability to produce atomic H but promoted electron transfer and thus altered the relative contributions of atomic H and electron transfer to the CE dechlorination, resulting in different reactivities and selectivities. These were indicated by the correlations of CE dechlorination rates and improvements with CE molecular descriptors, H 2 evolution rates, and electron transfer indicators of SNZVI. These mechanistic insights indicate the importance of determining the structure-specific properties and reactivity of both SNZVI materials and their target contaminants and can lead to a more rational design of SNZVI for in situ groundwater remediation of various CEs.

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