Mineralization of Ni²⁺-Bearing Mn Oxide through Simultaneous Sequestration of Ni²⁺ and Mn²⁺ by Enzymatically Active Fungal Mn Oxides

A fungus, Acremonium strictum KR21-2, produces biogenic manganese oxides (BMOs) that can oxidize exogenous Mn2+ ions to form different BMO phases. When other guest ions are present during the BMO formation, it can strongly affect the mineralogical characteristics of the resultant BMO phase. The impact of coexisting Ni2+ ions on the mineralogy of BMO phases formed through enzymatic Mn(II) oxidation and its sequestration ability is not yet fully understood. To better understand it, repeated sequestration experiments were conducted using BMOs in Ni2+/Mn2+ binary, single Ni2, and single Mn2+ solution systems with a pH range of 6.0 to 7.5. It was observed that simultaneous sequestration of Ni2+ and Mn2+ was efficient, with irreversible Ni2+ incorporation at pH values above 7.0. The resultant BMO phases showed that Ni2+-bearing Mn oxides resembling feitknechitite (β-MnOOH) were developed through enzymatic Mn(II) oxidation. At pH values below 6.5, the turbostratic birnessite structure was maintained even in Ni2+/Mn2+ binary solutions, and subsequently, the Ni2+ sequestration efficiency was low. The pseudo-first-order rate constants of enzymatically inactivated BMOs for Mn2+ sequestration were two orders of magnitude lower than those of active BMOs, indicating the crucial role of the enzymes in precipitating Ni2+-bearing Mn oxide phases. These findings provide new insights into the mechanism of Ni2+ interaction with Mn oxide through microbial activity under circumneutral pH conditions.