Towards the Recovery of By-Product Metals from Mine Wastes: An X-Ray Absorption Spectroscopy Study on the Binding State of Rhenium in Debris from a Centennial Iberian Pyrite Belt Mine

Rhenium is a very scarce element, occurring in the Earth's crust mainly carried by molybdenite (MoS2). Due to a very low availability comparative to actual industrial demand, rhenium is nowadays one of the most expensive mineral commodities and an increased interest is focused on ex- ploring residues resulting from a long-term mining, particularly of sulphide ore deposits. It is therefore noteworthy to assign the presence of rhenium (in a concentration up to 3 ppm) in the waste materials from the old sulphur factory at the abandoned mine of Sao Domingos (Iberian Pyrite Belt, Southeast Portugal), exploited since the Roman occupation of Iberia. Aiming at a potential sustainable recovery of rhenium as a by-product, X-ray near-edge absorption spectroscopy (XANES) was applied to clarify the Re-binding and mode of occurrence by comparing Re L3-edge XANES spectra obtained from mine waste samples (previously fully characterized by X-ray laboratory techniques) with similar spectra collected from Re-rich molybdenites (Mo1-xRexS2) and from Re-O model compounds configuring various valences and coordination environments of rhenium ions. Obtained results are commented, ruling out a possible Re-S binding and rather conforming with the binding of rhenium to oxygen in the analysed mine waste materials.