Argillization processes at the El Berrocal analogue granitic system (Spain): mineralogy,isotopic study and implications for the performance assessment of radwaste geological disposal

The El Berrocal granite/U-bearing quartz vein (UQV) system has been studied as a natural analogue of a high-level radioactive waste repository. The main objective was to understand the geochemical behaviour of natural nuclides under different physicochemical conditions. Within this framework, the argillization processes related to fracturing and formation of the uranium–quartz vein were studied from a mineralogical and isotopic standpoint in order to establish their temperatures of formation and thus complete the geothermal history of the system. For this purpose, δ¹⁸O values were determined for pure mineral from the unaltered granite and quartz from the uranium–quartz vein, as well as for mixture samples from the hydrothermally altered granite (sericitised granite) and clayey samples from fracture fillings, including the clayey walls of the uranium–quartz vein. The isotopic signature of quartz from the uranium–quartz vein and the monophasic nature of its fluid inclusions led us to conclude that the isotopic signature of water in equilibrium with quartz was approximately in the range from ?8.3‰ to ?5.7‰ V-SMOV, its temperature of formation being around 85–120 °C. The δ¹⁸O values of pure sericite from the hydrothermally altered granite, calculated by means of the oxygen fraction molar method, indicate that its temperature of formation, in equilibrium with the aforementioned waters, is also in the range from 70 °C to approximately 120 °C. Clays from fracture fillings and clayey walls of the uranium–quartz vein are usually mixtures, in different proportions, of illite, approximately formed between 70 and 125 °C; two generations of kaolinite formed at approximately 90–130 °C and at around 25 °C, respectively; smectite, formed at ≤25 °C; and occasionally palygorskite, formed either between 30 and 45 °C or 19 and 32 °C, depending on the fractionation equation used. These data suggest that sericite from the hydrothermally altered granite, quartz from the uranium–quartz vein, illite and the first generation of kaolinite from the fracture fillings resulted from the same hydrothermal process affecting the El Berrocal granite in relation to fracturing. Under certain physicochemical conditions (T≈100 °C, pH≈8 and log H₄SiO₄] between ?4 and ?3), illite and kaolinite can be paragenetic. As a result of weathering processes, smectite was formed from hydrothermal illite and inherited albite under alkaline weathering, while the second generation of kaolinite was formed from smectite, under acid conditions and close to the sulphide-rich uranium–quartz vein. Palygorskite is an occasional mineral formed probably either during the thermal tail of the above-described hydrothermal process or during weathering processes. In both cases, palygorskite must have formed from alkaline Si–Mg-rich solutions. Finally, these data and processes are discussed in terms of natural analogue processes, drawing some implications for the performance assessment of a deep geological radwaste repository (DGRR).