Mineral surface-catalyzed oxidation of Mn(II) by bromate: Implications for the occurrence of Mn oxides on Mars

Abstract

The occurrence of manganese (Mn) oxides on Mars is believed to be an indicator of an O2-rich paleoenvironment of Mars because Mn oxides often form through the oxidation of Mn(II) by O2 on the surface of Earth. An alternative formation pathway was recently proposed, in which Mn(II) is oxidized by bromate (BrO3−), a common oxidant in contemporary Martian regolith. However, the oxidation of Mn(II) by bromate in solution is kinetically controlled and slow unless using very high concentrations (100 mM) of reactants that may be irrelevant to the conditions of Mars. We conducted laboratory simulations to determine whether iron (Fe) oxides (hematite and goethite) and a phyllosilicate (montmorillonite), abundant minerals on the surface of Mars, could catalyze the oxidation of Mn(II) by bromate. Hematite and goethite, but not montmorillonite, dramatically accelerated the oxidation with a low concentration (1 mM) of Mn(II) and bromate under various solution conditions. The reaction system was autocatalytic with Fe oxides initiating the oxidation of Mn(II) at the early stage and the subsequent catalysis mainly provided by the Mn oxide products. In contrast to producing Mn(IV)O2 only during the homogeneous oxidation of Mn(II) by bromate in solutions, the heterogeneous mineral-surface catalyzed oxidation resulted in a mixture of Mn(III)OOH and Mn(IV)O2 phases. Mn(III)OOH was an intermediate product and can be further oxidized by bromate to Mn(IV)O2. The occurrence and accumulation of the intermediate product MnOOH can be attributed to its rapid formation due to surface-enhanced nucleation and growth on Fe oxide surfaces and to its higher resistance to oxidation by bromate than Mn(III) ions or clusters. Overall, mineral-surface catalyzed oxidation of Mn(II) by bromate is favorable from both thermodynamic and kinetic perspectives, and can be a major pathway for the occurrence of Mn oxides on Mars where microorganisms are lacking to catalyze the reaction. Our study further improves our understanding of the thermodynamic and kinetic controls on Mn(II) oxidation.