Natural source of Cr(VI) in soil: The anoxic oxidation of Cr(III) by Mn oxides.

Cr(VI) from oxidation of geogenic Cr(III) minerals is gradually becoming the primary source of Cr(VI) in soils and groundwater instead of direct emissions. Thermodynamically, natural oxidants of Cr(III) are limited to O2 and Mn oxides. The oxidation of Cr(III) occurs commonly in oxic soils but the difference in the oxidative dissolution of Cr(III) by Mn oxides in different redox soils (especially under anoxic conditions) is not fully understood and field evidence is lacking. Here, the relationship between Cr(VI) and Mn oxides in basalt-origin soil profiles under three different redox conditions (anoxic, suboxic and oxic) was studied. The oxidative dissolution of chromite was validated by synthesising δ-MnO2 that was close to biogenic Mn oxides under anoxic and oxic conditions. In anoxic soils, high levels of Cr(VI) were detected in the same horizons as those where Cr(III)-minerals co-existed with Mn(III/IV) oxides, suggesting an exclusive pathway for Cr(VI) generation through oxidation by Mn oxides where there was a deficiency of other oxidants, such as O2. In oxic soils, the highly abundant Fe oxides combined with Cr(III) to form Cr(III)-Fe(III) oxyhydroxides and Cr(VI) was generated mainly via slow oxidation by O2. The chromite oxidation experiment results also indicated that a high abundance of Mn oxides could promote chromite oxidative dissolution to generate Cr(VI), even under anoxic conditions. Additionally, the form of Cr and the reactivity and abundance of Mn oxides and reducing agents controlled the net content of Cr(VI) in the soil. This study showed that, even under reducing conditions, Cr(III) is readily oxidised by Mn oxides to generate Cr(VI) in reductant-deficient and Mn-rich soils, which may lead to the continuous introduction of Cr(VI) into groundwater and agricultural soils.