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.

The spatial organisation of swelling clay platelets in a suspension depends on the chemical composition of the equilibration solution. Individual clay platelets can be well dispersed, with surfaces entirely in contact with the external solution, or be stacked in tactoids, where part of the surfaces forms parallel alignments embedding interlayer water and cations. External and interlayer surfaces do not exhibit similar affinities for cations having different hydration and charge properties and the clay platelet stacking arrangement influences the clay affinity for these cations. This paper aims to establish the link between exchange properties and clay tactoid size and organisation for Na-Ca exchange on montmorillonite. Different montmorillonite samples behave differently with regards to Na-Ca exchange, from ideal to non-ideal exchange behaviour. A simple model coupling the tactoid stacking size to different Na/Ca relative affinities of the external and interlayer clay surfaces enables these differences to be reproduced.

Na/K, Na/Ca and Na/Mg exchange isotherms were performed on the fine fraction (<2 lm) of Imt-2 illite samples at a total normality of about 0.005 mol/L in anionic chloride medium. The derived selectivity coefficients for Na/K, Na/Ca and Na/Mg were found to vary as a function of the exchanger composition and compared well with the data collected in the literature for similar experimental conditions. Two models were built to reproduce the data: the first was a multi(2)-site model with constant Gaines and Thomas selectivity coefficients; the second was a one-site model taking into account surface species activity coefficients. The results of the models were in rather good agreement with both our data and literature data. The multi-site model proved to be efficient in predicting the exchanger composition as a function of the Na/Ca/Mg/K concentrations in solution, whereas the one-site model proved to be a better approach to derive the Na/ Ca/Mg/K concentrations in solution based on the knowledge of the exchanger composition and the total normality of the solution. The interest of this approach is illustrated by the need for major cation solute concentration predictions in compacted clay for the characterization of nuclear deep disposal host rock repositories.

Natural analogues studies have received growing interest during preceding years in a CCS perspective. There is a strong willing to deploy robust and reliable technologies to ensure the safety and integrity of CO 2 underground storages. Here we present a dataset acquired in the Eifel volcanic district, using geochemical monitoring methods focusing on both dissolved and gaseous species.Onshore and offshore monitoring (Lake Laacher See) were performed to depict spatial behaviour of CO 2 natural releases. Additional gaseous species, mainly helium and radon, were also monitored to better assess the shapes of gas vents, using methodologies that were learned from hydrological and tectonic applications. Lake water monitoring allowed the characterisation of the water body itself, in terms of lateral heterogeneities, to evaluate the impact of CO 2 deep degassing near the bottom of the lake. The use of a dedicated sensor for monitoring in situ CO 2 partial pressure did not provide more valuable information that was learned from more classical physico-chemical parameters. From those investigations, the usefulness of geochemical monitoring is still demonstrated, but the use of complementary approaches and methods is still needed to get a powerful set of techniques able to warn in case of leakages occurring from depth.