Green rust sulfate transformation under the impact of Cr(VI) and oxalic acid: Mechanism and environmental significance

Green rust (GR), as one of mixed-valent iron [Fe(II)-Fe(III)] minerals, has received a significant attention in recent years because it is an intrinsic and essential part of biogeochemical cycling of heavy metals and DOM. The transformation of GR is a key factor in altering the environmental behavior of heavy metals, and therefore, prediction of such transformation is critical for managing environmental quality. DOM and heavy metals are recognized to have a significant impact on iron oxide transformation. However, detailed information on these phenomena and mechanisms are still limited. In this study, Cr(VI) and oxalic acid (OA) widely distributed in the natural environment were selected representatives of heavy metals and DOM. The mechanism of their influence on GR transformation and their environmental significance were clarified. GR transformed to feroxyhyte under the impact of Cr(VI) and OA, and feroxyhyte did not transform to more crystalline iron oxides after 7 days. However, OA enhanced Fe dissolution and Cr(VI) reduction while weakening the immobilization of Cr on GR. SEM results demonstrated that OA addition resulted in the collapse of the feroxyhyte structure. SEM-EDS data indicated that Cr and OA were adsorbed on GR, suggesting that this can be an essential pathway for C and Cr sequestration during GR transformation. This study reveals Cr(VI) not only favors the formation of feroxyhyte, but also stabilizes the mineral to prevent transformation and meanwhile indicates the mechanisms of organic matter interactions with iron oxide and the environmental behavior of C and Cr during the iron oxide transformation processes.