Au sein des études menées par l'ANDRA pour caractériser le Callovo-Oxfordien, la chimie de l'eau interstitielle constitue une thématique clé car elle détermine le devenir dans le temps des matériaux introduit sur les sites de stockage (bentonite, béton, métaux, colis de verre). Elle détermine aussi la spéciation (et donc la mobilité) des radionucléides. La méthode développée dans le cadre du projet THERMOAR permet l'acquisition d'un jeu complet de données pour modéliser la chimie des eaux à partir de carottes de roche. Elle nécessite une étude minéralogique approfondie, un modèle de répartition eau libre/eau liée, des expériences de lessivage, des mesures des ions adsorbés, l'acquisition de constantes d'échange d'ions, la mesure des pressions partielles en CO 2. L'ensemble de ces expériences et mesures a été appliqué à des échantillons provenant du site du laboratoire Meuse/Haute-Marne et des forages régionaux de l'ANDRA. On observe ainsi la stabilité régionale d'un grand nombre de paramètres à l'exception d'une diminution de teneur en Na et Cl suivant un axe nord-est / sud-ouest passant par le laboratoire. Le modèle d'équilibre eau/roche permet de calculer la composition chimique des eaux interstitielle de la formation.

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Sodium‐K, Na‐Ca, Na‐Mg, and Na‐Sr exchange isotherms were performed at a total Cl concentration of about 0.005 mol L−1 on the fine fraction (<2 μm) of MX80 montmorillonite, mixed‐layer illite smectite minerals (IS), and clayey stones from European underground research laboratories. The derived selectivity coefficients for Na‐K, Na‐Ca, Na‐Mg, and Na‐Sr were found to vary very significantly as a function of the exchanger composition. A model was built to reproduce the data, taking into account the change of selectivity coefficient as a function of the exchanger composition of smectite. Model parameters were fitted using data from the present study and data from the literature obtained on smectite minerals. The addition of parameters for cation–anion pairs was found to improve the fitting results. The model was then successfully tested to reproduce published cation‐exchange features on natural clayey materials and soils suspended in fresh or saline water. Finally, it is shown that the simple combination of this smectite exchange model with a previously published illite exchange model is quite successful although perfectible in reproducing exchange data on IS.

In the coastal multilayer aquifer system of a highly urbanized southern city (Recife, Brazil), where groundwaters are affected by salinization, a multi-isotope approach (Sr, B, O, H) was used to investigate the sources and processes of salinization. The high diversity of the geological bodies, built since the Atlantic opening during the Cretaceous, highly constrains the heterogeneity of the groundwater chemistry, e.g. Sr isotope ratios, and needs to be integrated to explain the salinization processes and groundwater pathways. A paleoseawater intrusion, most probably the 120 kyB.P. Pleistocene marine transgression, and cationic exchange are clearly evidenced in the most salinized parts of the Cabo and Beberibe aquifers. All (87)Sr/(86)Sr values are above the past and present-day seawater signatures, meaning that the Sr isotopic signature is altered due to additional Sr inputs from dilution with different freshwaters, and water-rock interactions. Only the Cabo aquifer presents a well-delimitated area of Na-HCO3 water typical of a freshening process. The two deep aquifers also display a broad range of B concentrations and B isotope ratios with values among the highest known to date (63-68.5‰). This suggests multiple sources and processes affecting B behavior, among which mixing with saline water, B sorption on clays and mixing with wastewater. The highly fractionated B isotopic values were explained by infiltration of relatively salty water with B interacting with clays, pointing out the major role played by (palaeo)-channels for the deep Beberibe aquifer recharge. Based on an increase of salinity at the end of the dry season, a present-day seawater intrusion is identified in the surficial Boa Viagem aquifer. Our conceptual model presents a comprehensive understanding of the major groundwater salinization pathways and processes, and should be of benefit for other southern Atlantic coastal aquifers to better address groundwater management issues.