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 FeS2 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 FeS2, the Cr(VI) removal efficiency by FeS2 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.