Rare earth element enriched birnessite in water-bearing fractures, the Ytterby mine, Sweden

- The formation of secondary manganese oxides exceptionally enriched in rare earth elements is established.
- The main component is a birnessite-type MnO2into which the REE are firmly incorporated even at pH as low as 1.5.
- There is a strong preference for the trivalent REE in the mineral structure over divalent and monovalent metals.
- The influence of microorganisms in the accumulation of these Mn oxides is demonstrated by EPR-spectroscopy analysis.

Characterization of a black substance exuding from fractured bedrock in a subterranean tunnel revealed a secondary manganese oxide mineralisation exceptionally enriched in rare earth elements (REE). Concentrations are among the highest observed in secondary ferromanganese precipitates in nature. The tunnel is located in the unsaturated zone at shallow depth in the former Ytterby mine, known for the discovery of yttrium, scandium, tantalum and five rare earth elements.Elemental analysis and X-ray diffraction of the black substance establish that the main component is a manganese oxide of the birnessite type. Minor fractions of calcite, other manganese oxides, feldspars, quartz and about 1% organic matter were also found, but no iron oxides were identified. The Ytterby birnessite contains REE, as well as calcium, magnesium and traces of other metals. The REE, which constitute 1% of the dry mass and 2% of the metal content, are firmly included in the mineral structure and are not released by leaching at pH 1.5 or higher. A strong preference for the trivalent REE over divalent and monovalent metals is indicated by concentration ratios of the substance to fracture water. The REE-enriched birnessite has the general formula Mx(Mn3+,Mn4+)2O4·(H2O)n with M = (0.37-0.41) Ca + 0.02 (REE + Y), 0.04 Mg and (0.02-0.03) other metals, and with [Mn3+]/[Mn4+] = 0.86-1.00.The influence of microorganisms on the accumulation of this REE enriched substance is demonstrated by electron paramagnetic resonance spectroscopy. Results show that it is composed of two or more manganese phases, one of which has a biogenic signature. In addition, the occurrence of C31 to C35 extended side chain hopanoids among the identified lipid biomarkers combined with the absence of ergosterol, a fungal lipid biomarker, indicate that the in-situ microbial community is bacterial rather than fungal.