Interaction between chromite and Mn(II/IV) under anoxic, oxic and anoxic-oxic conditions: Dissolution, oxidation and pH dependence

Abstract

Chromite oxidative dissolution has been recognized as an important process leading to elevated Cr(VI) in soil and groundwater. Under natural conditions, direct oxidation of Cr(III) by O2 is very unfavorable, and a critical determinant of Cr(VI) generation in soil and groundwater is the interaction between chromite and Mn(II) or Mn(III/IV) oxides. Here, the effects of Mn(II) or Mn(IV) on the oxidative dissolution of chromite were investigated at pH values of 5, 7 and 9 during anoxic, oxic and anoxic-oxic processes. The results showed that the direct oxidation of Cr(III) by O2 was slow in aqueous-phase system, while the Mn oxides in chromite could oxidize dissolved Cr(III). The added Mn(II) can be catalytically oxidized to MnOOH on the chromite surface only under alkaline oxidation conditions, and the catalytic efficiency is slow, which has less effect on chromite oxidative dissolution. Compared with the direct oxidation of O2 and catalytic oxidation of Mn(II), the synthesized biogenic Mn oxides drove the oxidative dissolution of chromite to release more Cr(VI) and were the main threat to the long-term stability of chromite in the environment. Overall, both acidic and alkaline environments are favorable to the catalytic oxidation of chromite by O2, Mn(II) and δ-MnO2, while neutral conditions are favorable to the long-term stability of chromite. These above processes may occur in soils and sediments with redox fluctuations (e.g., rice paddies, river floodplains, wetlands, and peatlands), and the presence of Mn(II) and Mn(III/IV) may play an important role in the oxidation and mobilization of Cr(III), leading to elevated Cr(VI) levels in soils and groundwater.