Synergistic removal of Cr(VI) by S-nZVI and organic acids: The enhanced electron selectivity and pH-dependent promotion mechanisms

The effects of organic acids on hexavalent chromium (Cr(VI)) removal by reduced iron-based materials have been extensively studied. Nevertheless, the promotion mechanism from the perspective of the electron transfer process is still unclear. Herein, sulfidated nanoscale zero-valent iron (S-nZVI) and the selected organic acids, citric acid (containing both -OH and −COOH groups) and oxalic acid (containing only −COOH groups), showed significant synergistic promotion effects in Cr(VI) removal. The FeS and FeS 2 on S-nZVI surface could enhance the Cr(VI) reduction as the reductive entity and electron conductor. Furthermore, even though the reactivity of FeS with Cr(VI) is higher than that with FeS 2 , the Cr(VI) removal efficiency by FeS 2 was much higher than that by FeS with organic acids. Under neutral and alkaline conditions (pH 6.0–8.0), organic acids promoted the diffusion, adsorption and complexation of Cr(VI) on S-nZVI surface, thus enhancing the electron selectivity towards Cr(VI). However, when the solution pH changed to acidic conditions (pH 4.0), organic acids facilitated the dissolution of Fe(II) ions from S-nZVI and enhanced the electron utilization towards Cr(VI) via the fast Fe(III) reduction process. This study provided a new insight into the Cr(VI) removal, which was beneficial to understand the application boundaries of S-nZVI for Cr(VI) remediation.