Ligand-Assisted Formation of Soluble Mn(III) and Bixbyite-like Mn2O3 by Shewanella putrefaciens CN32

Functional material synthesis through biomineralization is effective and environmentally friendly. Biomineralized manganese (Mn) oxides are important for remediation and energy storage. Manganese(II) biomineralization is achieved by a diverse group of bacteria. We show that in the presence of oxygen the dissimilatory manganese-reducing bacterium Shewanella putrefaciens CN32 can oxidize Mn(II). The Mn(II) oxidation was accelerated with the increase in the initial Mn(II) concentration from 0.5 to 3 mM. The reaction was mainly associated with a cell-free filtrate, rather than the direct enzymatic oxidation or indirect oxidation by reactive oxygen species or macrocyclic siderophores. Instead, indirect oxidization of Mn(II) into soluble Mn(III) and bixbyite-like Mn2O3 via microbially produced extracellular ligands (molecular weights of 1-3 kDa) was identified. This work broadens our view about microbial Mn(II) oxidation and unveils the important roles of Shewanella species in the geochemical cycling of manganese.