ABSTRACT
Sulfidated nanoscale zerovalent iron (S-nZVI) is a promising reductant for trichloroethylene in groundwater, yet a comprehensive understanding of its degradation efficiency for other chlorinated hydrocarbons (CHCs) is lacking. In this study, we assessed the benefits of using S-nZVI for the degradation of two chlorinated methanes, three chlorinated ethanes, and four chlorinated ethenes compared to unamended nZVI, by analyzing the degradation rate constants, the maximum degradation quantity, and the degradation pathways and products under both stoichiometrically electron excess and limited conditions. The improvement in rate constants induced by sulfidation was compound specific and was more significant for chlorinated ethenes (57-707 folds) than for the other CHCs (1.0-17 folds). This is likely because of the different reduction mechanisms of each CHC and sulfidation may favor specific mechanisms associated with the reduction of chlorinated ethenes more than the others. Sulfidation of nZVI enabled either higher (3.1-24.4 folds) or comparable (0.78-0.91) maximum degradation quantity, assessed under electron limited conditions, for all the CHCs investigated, indicating the promise of S-nZVI for remediation of groundwater contaminated by CHC mixtures. Furthermore, we proposed the degradation pathways of various CHCs based on the observed degradation intermediates and products and found that sulfidation suppressed the generation of partially dechlorinated products, particularly for chlorinated methanes and ethanes, and favor degradation pathways leading to the non-chlorinated benign products. This is the first comprehensive study on the efficacy of sulfidation in improving the degradation of a suite of CHCs and the results provide valuable insight to the assessment of applicability and benefits of S-nZVI for CHC remediation.
