Dechlorination of Excess Trichloroethene by Bimetallic and Sulfidated Nanoscale Zero-Valent Iron

Nanoscale zerovalent iron (nZVI) likely finds its application in source zone remediation. Two approaches to modify nZVI have been reported: bimetal (Fe-Me) and sulfidated nZVI (S-nZVI). However, previous research has primarily focused on enhancing particle reactivity with these two modifications under more plume-like conditions. In this study, we systematically compared the trichloroethene (TCE) dechlorination pathway, rate, and electron selectivity of Fe-Me (Me: Pd, Ni, Cu, and Ag), S-nZVI, and nZVI with excess TCE simulating source zone conditions. TCE dechlorination on Fe-Me was primarily via hydrogenolysis while that on S-nZVI and nZVI was mainly via beta-elimination. The surface-area normalized TCE reduction rate (k(SA)') of Fe-Pd, S-nZVI, Fe-Ni, Fe-Cu, and Fe-Ag were , similar to 6800-, 190-, 130-, 20-, and 8-fold greater than nZVI. All bimetallic modification enhanced the competing hydrogen evolution reaction (HER) while sulfidation inhibited HER. Fe-Cu and Fe-Ag negligibly enhanced electron utilization efficiency (epsilon(e)) while Fe-Pd, Fe-Ni, and S-nZVI dramatically increased epsilon(e) from 2% to similar to 100%, 69%, and 72%, respectively. Adsorbed atomic hydrogen was identified to be responsible for the TCE dechlorination on Fe-Me but not on S-nZVI. The enhanced dechlorination rate along with the reduced HER of S-nZVI can be explained by that FeS conducting major electrons mediated TCE dechlorination while Fe oxides conducting minor electrons mediated HER.