Effects of Sulfidation and Nitrate on the Reduction of N-Nitrosodimethylamine by Zerovalent Iron

Competition among oxidizing species in groundwater and wastewater for the reductive capacity of zerovalent iron (ZVI) makes the selectivity of ZVI for target contaminant degradation over other reduction pathways a major determinant of the feasibility of ZVI-based water treatment processes. The selectivity for reduction of contaminants over water is improved by sulfidation, but the effect of sulfidation on other competing reactions is not known. The interaction between these competing reactions was investigated using N-nitrosodimethylamine (NDMA) as the target contaminant, nitrate as a co-contaminant, and micrometer-sized ZVI with and without sulfidation. Unsulfidated ZVI reduced NDMA to dimethylamine via N,N-dimethylhydrazine, but the addition of nitrate decreased the rate of NDMA reduction and increased the quantity of intermediate observed. With sulfidated ZVI, the kinetics and products of NDMA reduction were similar to those with unsulfidated ZVI, but no inhibitory effect of nitrate was observed. Conversely, the reduction of nitrate - which dominated NDMA reduction in unsulfidated ZVI systems - was strongly inhibited by sulfidation. H₂ and Fe²⁺ generation by sulfidated ZVI was almost independent of nitrate concentration. Therefore, sulfidation improved the efficiency of NDMA reduction by ZVI in the presence of nitrate mainly by inhibiting nitrate reduction. The shift in selectivity of ZVI for NDMA over nitrate upon sulfidation was due to replacement of Fe⁰/Fe_xO_y surface sites with FeS.