Different Pathways for Cr(III) Oxidation: Implications for Cr(VI) Reoccurrence in Reduced Chromite Ore Processing Residue.

Hexavalent chromium contamination is a global environmental issue and usually reoccurs in alkaline reduced chromite ore processing residues (rCOPR). The oxidation of Cr(III) solids in rCOPR is one possible cause but as yet little studied. Herein, we investigated the oxidation of Cr(OH), a typical species of Cr(III) in rCOPR, at alkaline pH (9-11) with δ-MnO under oxic/anoxic conditions. Results revealed three pathways for Cr(III) oxidation under oxic conditions: (1) oxidation by oxygen, (2) oxidation by δ-MnO, and (3) catalytic oxidation by Mn(II). Oxidations in the latter two were efficient, and oxidation via Pathway 3 was continuous and increased dramatically with increasing pH. XANES data indicated feitknechtite (β-MnOOH) and hausmannite (MnO) were the reduction products and catalytic substances. Additionally, a kinetic model was established to describe the relative contributions of each pathway at a specific time. The simulation outcomes showed that Cr(VI) was mainly formed via Pathway 2 (>51%) over a short time frame (10 days), whereas in a longer-term (365 days), Pathway 3 predominated the oxidation (>78%) with an increasing proportion over time. These results suggest Cr(III) solids can be oxidized under alkaline oxic conditions even with a small amount of manganese oxides, providing new perspectives on Cr(VI) reoccurrence in rCOPR and emphasizing the environmental risks of Cr(III) solids in alkaline environments.