Sulfidation mitigates the passivation of zero valent iron at alkaline pHs: Experimental evidences and mechanism

Groundwater pH is one of the most important geochemical parameters in controlling the interfacial reactions of zero-valent iron (ZVI) with water and contaminants. Ball milled, microscale ZVI (mZVI^bm) efficiently dechlorinated TCE at initial stage (<24 h) at pH 6-7 but got passivated at later stage due to pH rise caused by iron corrosion. At pH > 9, mZVI^bm almost completely lost its reactivity. In contrast, ball milled, sulfidated microscale ZVI (S-mZVI^bm) didn't experience any reactivity loss during the whole reaction stage across pH 6-10 and could efficiently dechlorinate TCE at pH 10 with a reaction rate of 0.03 h^-1. Increasing pH from 6 to 9 also enhanced electron utilization efficiency from 0.95% to 5.3%, and from 3.2% to 22%, for mZVI^bm and S-mZVI^bm, respectively. SEM images of the reacted particles showed that the corrosion product layer on S-mZVI^bm had a puffy/porous structure while that on mZVI^bm was dense, which may account for the mitigated passivation of S-mZVI^bm under alkaline pHs. Density functional theory calculations show that covered S atoms on the Fe(100) surface weaken the interactions of H₂O molecules with Fe surfaces, which renders the sulfidated Fe surface inefficient for H₂O dissociation and resistant to surface passivation. The observation from this study provides important implication that natural sulfidation of ZVI may largely contribute to the long-term (>10 years) efficiency of TCE decontamination by permeable reactive barriers with pore water pH above 9.