X-ray absorption near edge structure (XANES) spectroscopy was used on zoned sphalerites (ZnS) from two world-class Mississippi Valley Type deposits, the Central and Eastern Tennessee Mining district, USA, in order to investigate germanium oxidation states. Due to the low germanium concentrations of these samples, it was necessary to perform the X-ray absorption spectroscopy (XAS) in fluorescence mode. The overlapping of the Zn Kβ and Ge Kα emission lines meant that a high energy-resolution was required. This was achieved using crystal analysers and allowed a bandwidth of 1.3 eV to be obtained. Experimental spectra were compared to XANES calculations and three configurations of germanium incorporation into sphalerite were identified. The first two, the most prevalent, show germanium (II) and (IV) surrounded by sulphur atoms in tetrahedral coordination, suggesting the replacement of Zn by Ge. In the third configuration, germanium (IV) is surrounded by oxygen atoms. This third configuration is unexpected for a zinc sulphide mineral and it resembles that of argutite (GeO₂).

The oxidation of pyrite is one of the near field processes of the chemical evolution of clay rock planned to host a deep geological radioactive waste repository during operation. Indeed, this process can lead to transitory acidic conditions in the medium (i.e., production of sulphuric acid, carbonic acid) which may influence the corrosion kinetics of the carbon steel components of some disposal cells. In order to improve the geochemical modelling of the long-term disposal, the oxidation of pyrite in contact with clays and carbonates at 100 °C must be evaluated. In this study, special attention was paid to the pyrite oxidation rate thanks to an original experimental set-up, involving several pyrite/mineral mixtures and a reactor coupled to a micro gas chromatograph (P_O2 and P_CO2 monitoring). Although thermodynamic modelling expects that hematite is the most stable phase in a pure pyrite heated system (low pH), experiments show the formation of native sulfur as an intermediate product of the reaction. In the presence of calcite, the pH is neutralized and drives the lower reactivity of pyrite in the absence of native sulfur. The addition of clay phases or other detrital silicates from the claystone had no impact on pyrite oxidation rate. The discrepancies between experiments and thermodynamic modelling are explained by kinetic effects. Two laws were deduced at 100 °C. The first concerns a pure pyrite system, with the following law: $r_{Py}={10}^{-4.8}·P_{O_2}^{0.5}·t^{-0.5}$ . The second concerns a pyrite/carbonates system: $r_{Py+Ca}={10}^{-5.1}·P_{O_2}^{0.5}·t^{-0.5}$ where P_O2 corresponds to the partial pressure of O₂ (in bar) and t is time in seconds. Different mechanisms are proposed to explain the evolution with time of the O₂ consumption during pyrite oxidation: (i) decrease of the specific or reactive surface area after oxidation of fine grains of pyrite, (ii) decrease of O₂ pressure, (iii) growing up of secondary minerals (Fe-oxides or anhydrite in the presence of calcium in the system) on the surface of pyrite limiting the access of O₂ to the fresh surface of pyrite, and (iv) change in the pH of the solution.

Les gisements de type Mississippi Valley Type (MVT) du centre et de l’est du Tennessee, respectivement MTM (Middle Tennessee Mine) et ETM (East Tennessee Mine), renferment des réserves importantes de zinc sous forme de sphalerite, mais aussi de germanium en substitution du zinc dans la sphalerite. Cependant seuls les gisements du district de MTM contiennent des teneurs économiquement exploitables de germanium. Ces deux districts miniers, observés dans les mêmes formations géologiques et de minéralogies comparables, sont comparés afin de comprendre la distribution du germanium et des autres éléments traces dans les MVT. Les analyses à l’échelle de l’atome par spectroscopie d’absorption X, XANES et EXAFS, ont mis en évidence plusieurs configurations de germanium dans la sphalerite : le germanium peut être en substitution du zinc dans ZnS sous forme 2+ ou 4+, mais il peut aussi être sous forme d’oxyde de germanium en inclusions nanométriques dans la sphalerite. Les analyses à l’échelle du minéral, par microsonde électronique, LA-ICP-MS et spectroscopie Raman, ont mis en évidence deux groupes d’éléments traces : i) le premier composé des éléments Fe et Cd, est préférentiellement incorporé suivant les faces (110) de la sphalerite, ii) le second composé des éléments Cu, Ga et Ge, est préférentiellement incorporé suivant les faces (010) de la sphalerite. Le couplage de la spectroscopie Raman avec l’ablation laser ICP-MS a permis de mettre en évidence un partitionnement des éléments traces entre la forme cubique et hexagonale de ZnS : les éléments Fe et Cd sont plus concentrés dans la forme cubique, alors que les éléments Cu, Ga et Ge sont plus concentrés dans la forme hexagonale de ZnS