Microbially mediated formation of birnessite-type manganese oxides and subsequent incorporation of rare earth elements, Ytterby mine, Sweden

Sammanfattning: Microbes exert extensive control on redox element cycles. They participate directly orindirectly in the concentration and fractionation of elements by influencing the partitioningbetween soluble and insoluble species. Putative microbially mediated manganese (Mn) oxidesof the birnessite-type, enriched in rare earth elements (REE) + yttrium (Y) were recentlyfound in the Ytterby mine, Sweden. A poorly crystalline birnessite-type phyllomanganate isregarded as the predominant initial phase formed during microbial Mn oxidation. Owing to ahigher specific surface area, this biomineral also enhances the known sorption property of Mnoxides with respect to heavy metals (e.g. REE) and therefore has considerable environmentalimpact.The concentration of REE + Y (2±0.5% of total mass, excluding oxygen, carbon and silicon)in the Ytterby Mn oxide deposit is among the highest ever observed in secondary precipitateswith Mn and/or iron. Sequential extraction provides evidence of a mineral structure where theREE+Y are firmly included, even at pH as low as 1.5. Concentration ratios of Mn oxideprecipitates to fracture water indicate a strong preference for the trivalent REE+Y overdivalent and monovalent metals. A culture independent molecular phylogenetic approach wasadopted as a first step to analyze the processes that microbes mediate in this environment andspecifically how the microbial communities interact with the Mn oxides. Plausible players inthe formation of the investigated birnessite-type Mn oxides are mainly found within theferromanganese genera Hyphomicrobium and Pedomicrobium and a newly identified YtterbyBacteroidetes cluster most closely related to the Terrimonas. Data also indicate that thedetected microorganisms are related to the environmental constraints of the site including lowconstant temperature (8°C), absence of light, high metal content and possibly proximity to theformer storage of petroleum products.