Sulfidation extent of nanoscale zerovalent iron controls selectivity and reactivity with mixed chlorinated hydrocarbons in natural groundwater

Sulfidated nanoscale zerovalent iron (S-nZVI) exhibits low anoxic oxidation and high reactivity towards many chlorinated hydrocarbons (CHCs). However, nothing is known about S-nZVI reactivity once exposed to complex CHC mixtures, a common feature of CHC plumes in the environment. Here, three S-nZVI materials with varying iron sulfide (mackinawite, FeSm) shell thickness and crystallinity were exposed to groundwater containing a complex mixture of chlorinated ethenes, ethanes, and methanes. CHC removal trends yielded pseudo-first order rate constants (kobs) that decreased in the order: trichloroethene > trans-dicloroethene > 1,1-dichlorethene > trichloromethane > tetrachloroethene > cis-dichloroethene > 1,1,2-trichloroethane, for all S-nZVI materials. These kobs trends showed no correlation with CHC reduction potentials based on their lowest unoccupied molecular orbital energies (ELUMO) but absolute values were affected by the FeSm shell thickness and crystallinity. In comparison, nZVI reacted with the same CHCs groundwater, yielded kobs that linearly correlated with CHC ELUMO values (R2 = 0.94) and that were lower than S-nZVI kobs. The CHC selectivity induced by sulfidation treatment is explained by FeSm surface sites having specific binding affinities towards some CHCs, while others require access to the metallic iron core. These new insights help advance S-nZVI synthesis strategies to fit specific CHC treatment scenarios.