Epithermal Origin and Environmental Evolution of Iron-Hosted Thallium and Kerogen Deposits: The Lodares Area Case (Soria, Spain)

Hydrothermal pyrite is an important source of thallium (Tl) but this rare element can be also detected in the secondary iron goethite-lepidocrocite and jarosite ores, associated to hydrothermal kerogen, manganese oxides, accessorial potassium minerals and tiny Tl-bearing clusters shielded in quartz masses. We studied Tl-bearing samples collected from Fe-Mn ores hosted in dolostone rocks sited along ca. 15 km of fossil thermal springs following a geological fault in the Lodares surroundings. Samples were analyzed by environmental scanning electron microscopy and energy dispersive spectroscopy (ESEM-EDS), electron probe micro-analysis (EPMA), inductively coupled plasma-mass spectroscopy (ICP-MS), X-ray diffraction analysis (XRD), Tl LIII-edge X-ray absorption near-edge structure (XANES) spectroscopy, Micro-Raman and Fourier transform infrared spectroscopy (FTIR). We found epithermal pyrite, sphalerite, galena and baryte and secondary gypsum, jarosite, scorodite, anglesite, goethite, epsomite and elemental sulfur produced by both hydroxylation and bacterial processes. The highest Tl contents were found in hydrothermal pyrite (200 mg kg-1), kerogen (13 mg kg-1), manganese ores (27 mg kg-1) and iron sulfate-hydroxides (142 mg kg-1). The aquatic kerogen was formed in a marine environment and later heavily carbonized during the hydrothermal processes. The Lodares outcrops exhibit interesting details on the geochemical cycle of Tl in a genetic frame of epithermal formation of pyrite and kerogen.