Enhanced arsenic(III) sequestration via sulfidated zero-valent iron in aerobic conditions: Adsorption and oxidation coupling processes

Sulfidated zero-valent iron (S-ZVI) has shown significant potential for the removal of arsenic(III). However, little attention has been paid to the mechanism of As(III) sequestration enhancement and how the phase transformation for S-ZVI strengthens this process in aerobic conditions. In this work, sulfidated ZVI was created by ball-milling (S-ZVIbm) and liquid-mixing (S-ZVIlm) of ZVI with elemental sulfur(S0) to investigate the performance and mechanisms of As(III) sequestration in air-saturated water. Sulfidation was found to significantly enhance the As(III) removal rate constant, which was 2.8 ∼ 6.7 times (S-ZVIbm) and 3.1 ∼ 17.1 times (S-ZVIlm) higher than that without sulfidation. FeS was identified as the predominant sulfur species in the S-ZVI samples using S K-edge XANES spectra. The enhanced electron transfer and ZVI corrosion after sulfidation were verified via electrochemical tests. XANES and Mössbauer spectra suggested that lepidocrocite(γ-FeOOH) was the predominant corrosion product generated on the ZVI surface with the presence of oxygen, and DFT calculations further confirmed the improved performance of γ-FeOOH for As(III) sequestration. Besides, As(III) oxidation occurred dominantly on the heterogeneous surface rather than in solution, and the As(III) sequestration pathway of adsorption followed by oxidation was proposed. This study provides new insight into the enhanced As(III) sequestration by S-ZVI in aerobic conditions.