Simultaneous Sequestration of Co2+ and Mn2+ by Fungal Manganese Oxide through Asbolane Formation

Biogenic manganese oxides (BMOs) have attractive environmental applications owing to their metal sequestration and oxidizing abilities. Although Co readily accumulates into Mn oxide phases in natural environments, the Co2+ sequestration process that accompanies the enzymatic Mn(II) oxidation of exogenous Mn2+ remains unknown. Therefore, we prepared newly formed BMOs in a liquid culture of Acremonium strictum KR21-2 and conducted repeated sequestration experiments in a Mn2+/Co2+ binary solution at pH 7.0. The sequestration of Co2+ by newly formed BMOs (similar to 1 mM Mn) readily progressed in parallel with the oxidation of exogenous Mn2+, with higher efficiencies than that in single Co2+ solutions when the initial Co2+ concentrations (0.16-0.8 mM) were comparable to or lower than the exogenous Mn2+ concentration (similar to 0.8 mM). This demonstrates a synergetic effect on Co sequestration. Powder X-ray diffraction showed a typical pattern for asbolane only when newly formed BMOs were treated in Mn2+/Co2+ binary systems, implying that the enzymatic Mn(II) oxidation by newly formed BMOs favored asbolane formation. Cobalt K-edge X-ray absorption near-edge structure measurements showed that both Co(II) and Co(III) participated in the formation of the asbolane phase in the binary solutions, whereas most of the primary Co2+ was sequestered as Co(III) in the single Co2+ solutions, which partly explains the synergetic effects on Co sequestration efficiency in the binary solutions. The results presented here provide new insights into the mechanism of Co interaction with Mn oxide phases through asbolane formation by enzymatic Mn(II) oxidation under circumneutral pH conditions.