Metal Exchangeability in the REE-Enriched Biogenic Mn Oxide Birnessite from Ytterby, Sweden

A black substance exuding from fractures was observed in 2012 in Ytterby mine, Sweden, and identified in 2017 as birnessite with the composition M_x[Mn(III,IV)]₂O₄∙(H₂O)_n. M is usually calcium and sodium, with x around 0.5. The Ytterby birnessite is unique, with M being calcium, magnesium, and also rare earth elements (REEs) constituting up to 2% of the total metal content. The biogenic origin of the birnessite was established in 2018. Analysis of the microbial processes leading to the birnessite formation and the REE enrichment has continued since then. The process is fast and dynamic, as indicated by the depletion of manganese and of REE and other metals in the fracture water during the passage over the precipitation zone in the mine tunnel. Studies of the exchangeability of metals in the structure are the main objective of the present program. Exposure to solutions of sodium, calcium, lanthanum, and iron led to exchanges and altered distribution of the metals in the birnessite, however, generating phases with almost identical structures after the exchanges, and no new mineral phases were detected. Exchangeability was more efficient for trivalent elements (REE) over divalent (calcium) and monovalent (sodium) elements of a similar size (ionic radii 90–100 pm).