Sulfidation of Zero-Valent Iron by Direct Reaction with Elemental Sulfur in Water: Efficiencies, Mechanism, and Dechlorination of Trichloroethylene

Sulfidation can enhance both the reactivity and selectivity (i.e., electron efficiency, εe) of zero-valent iron (ZVI) in contaminant removal, which may make this technology cost-effective for a wider range of water treatment applications. However, current sulfidation methods involve either hazardous or unstable sulfidation agents (e.g., Na2S, Na2S2O3, and Na2S2O4) or energy-intensive preparations (e.g., mechanochemical sulfidation with elemental sulfur). In this study, we demonstrate that very efficient sulfidation of microscale ZVI (mZVI) can be achieved at all S/Fe molar ratios (∼100% sulfidation efficiency, εs) simply by direct reaction between elemental sulfur (S0) and ZVI in an aqueous suspension at ambient temperature. In comparison, the εs values obtained using Na2S, Na2S2O3, or Na2S2O4 as the sulfidation agents were only ∼23, ∼75, and ∼38%, respectively. The sulfidated mZVI produced using the new method reacts with trichloroethylene (TCE) with very high rates and electron efficiencies: rate constants and electron efficiencies were 800- and 79-fold higher than those of the unsulfidated mZVI. The enhanced performance of this material, together with the operational advantages of S0 for sulfidation (including safety, stability, and cost), may make it a desirable product for full-scale engineering applications.