Absorption mechanisms of Cu2+ on a biogenic bixbyite-like Mn2O3 produced by Bacillus CUA isolated from soil

Abstract

Although most reported biogenic Mn oxides are hexagonal birnessites, other types of biogenic Mn oxides also commonly occur in the environment. However, sorption characteristics and underlying mechanisms of the adsorption of heavy-metal ions on these biogenic Mn oxides are still rarely addressed. In this study, the sorption mechanisms of Cu(II) on a low valence biogenic Mn oxide, poorly crystallized bixbyite-like Mn₂O₃ (α-Mn₂O₃), were investigated.

The maximum adsorption capacity of Cu(II) onto this biogenic Mn oxide at pH?6.00 was 796?mmol/kg (0.45?mol Cu mol^?1 Mn). The complex structure of adsorbed Cu(II) was constrained using Cu extended X-ray absorption fine structure (EXAFS) analysis, combined with structural parameters of the biogenic Mn oxide with alternately arranged regular and distorted MnO₆ octahedra obtained through multiple-FEFF fitting of Mn EXAFS data. The sorbed Cu(II) was found to coordinate with the biogenic Mn oxide particle edges as inner-sphere complexes. At a relatively low Cu²⁺ loading (233?mmol/kg, pH?6.00), Cu(II) adsorbed onto the biogenic Mn oxide with two types of coordinated complexes, i.e., (1) coordinated with one regular/distorted MnO₆ octahedron as a monodentate-mononuclear complex and (2) with two adjacent MnO₆ octahedra as a bidentate-binuclear complex. While, at a relatively high Cu²⁺ loading (787?mmol/kg, pH?6.00), only one type of coordinated complex was constrained, the adsorbed Cu(II) coordinated with one regular/distorted MnO₆ octahedron as a monodentate-mononuclear complex.

This research extends further insight into the bacterial Mn(II) oxidation in the environment and serves as a good reference for understanding the interactions between metal ions and biogenic low valence Mn oxides, which are still poorly explored either theoretically or practically.