Genesis and supergene weathering of tetrahedrite-(Hg) in meta-carbonate rocks: Bearing on differential mobility of priority pollutant metals

The Cu-Sb-Hg mineralization of San Giuliano Terme (Monti Pisani, Tuscany, Italy) is characterized by the widespread occurrence of deeply altered tetrahedrite-(Hg) hosted within joints and faults in the Liassic “Calcari ceroidi” Formation. Through a multi-technique approach (optical and scanning electron microscopy, electron microprobe analysis, single-crystal and powder X-ray diffraction, micro-Raman spectroscopy, X-ray fluorescence, fluid inclusion analysis), tetrahedrite-(Hg) and its alteration products have been characterized and data about its genesis and successive supergene weathering have been collected. Tetrahedrite-(Hg) from San Giuliano Terme has the empirical formula Cu9.92Ag0.02(Hg1.64Fe0.30Zn0.04)Σ1.98(Sb3.53As0.56)Σ4.09S12.95, and is found with scarce gangue minerals represented by calcite, baryte, and very rare fluorite. The mineralization formed from hydrothermal fluids with moderately high salinity (~ 17.5 wt% NaClequiv.) of dominantly metamorphic origin at T ~ 285 °C. Tetrahedrite-(Hg) is usually fully replaced by a mixture of cinnabar, roméite-group minerals, malachite, and rarely azurite. Based on the modal abundance of the mineralogical constituents and their micro-textures, four stages of supergene weathering of tetrahedrite-(Hg) have been recognized. The alteration stages reflect the progressive ingression of meteoric water into the system, with consequent oxidation of tetrahedrite-(Hg) and the introduction of Ca2+, HCO3- and H2O, as well as the progressive removal of S, Sb, and Cu. The relative proportions of the supergene minerals in the four alteration stages can be taken as a proxy for the mobility of the main chemical constituents of tetrahedrite-(Hg), three of which (Hg, Sb, and Cu) are priority pollutant metals. Mercury was found to be the least mobile element in the reconstructed geochemical process. In fact, the widespread precipitation of cinnabar in the space formerly occupied by tetrahedrite-(Hg) hinders the dispersion of Hg in the environment, sequestering it in a solid matrix.