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, FeS_m) 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 (k_obs) 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 k_obs trends showed no correlation with CHC reduction potentials based on their lowest unoccupied molecular orbital energies (E_LUMO) but absolute values were affected by the FeS_m shell thickness and crystallinity. In comparison, nZVI reacted with the same CHCs groundwater, yielded k_obs that linearly correlated with CHC E_LUMO values (R² = 0.94) and that were lower than S-nZVI k_obs. The CHC selectivity induced by sulfidation treatment is explained by FeS_m 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.