Aqueous Co removal by mycogenic Mn oxides from simulated mining wastewaters

Naturally occurring manganese (Mn) oxide minerals often form by microbial Mn(II) oxidation, resulting in nanocrystalline Mn(III/IV) oxide phases with high reactivity that can influence the uptake and release of many metals (e.g., Ni, Cu, Co, and Zn). During formation, the structure and composition of biogenic Mn oxides can be altered in the presence of other metals, which in turn affects the minerals' ability to bind these metals. These processes are further influenced by the chemistry of the aqueous environment and the type and physiology of microorganisms involved. Conditions extending to environments that typify mining and industrial wastewaters (e.g., increased salt content, low nutrient, and high metal concentrations) have not been well investigated thus limiting the understanding of metal interactions with biogenic Mn oxides. By integrating geochemistry, microscopic, and spectroscopic techniques, we examined the capacity of Mn oxides produced by the Mn(II)-oxidizing Ascomycete fungus Periconia sp. SMF1 isolated from the Minnesota Soudan Mine to remove the metal co-contaminant Co(II) from synthetic waters that are representative of mining wastewaters currently undergoing remediation efforts. We compared two different applied remediation strategies under the same conditions: coprecipitation of Co with mycogenic Mn oxides versus adsorption of Co with pre-formed fungal Mn oxides. Co(II) was effectively removed from solution by fungal Mn oxides through two different mechanisms: incorporation into, and adsorption onto, Mn oxides. These mechanisms were similar for both remediation strategies, indicating the general effectiveness of Co(II) removal by these oxides. The mycogenic Mn oxides were primarily a nanoparticulate, poorly-crystalline birnessite-like phases with slight differences depending on the chemical conditions during formation. The relatively fast and complete removal of aqueous Co(II) during biomineralization as well as the subsequent structural incorporation of Co into the Mn oxide structure illustrated a sustainable cycle capable of continuously remediating Co(II) from metal-polluted environments.