Interaction of Tournemire argillite (Aveyron, France) with hyperalkaline fluids: Batch experiments performed with powdered and/or compact materials

Abstract Argillaceous rocks and concrete matrix are considered as potential host rocks and engineered barrier, respectively for radioactive waste repositories. The concrete matrix could react with the groundwater of the geological site, inducing a drastic change in its chemical composition and pH. Consequently, the physico-chemical properties of the rock in contact with this hyperalkaline fluid may be modified. Therefore, an experimental programme has been developed for examining the physico-chemical changes of claystone in contact with alkaline fluids: batch experiments undertaken as a preliminary step followed by diffusion and percolation experiments in order to describe and to assess the physico-chemical phenomena observed under repository conditions. The first series of batch experiments are carried out in order to study the degradation of the Tournemire argillite properties caused by a fluid resulting from a contact with fresh concrete, considered as the most aggressive in relation to its hyper alkaline pH (≈13). Thus, the influence of several parameters is tested, such as liquid/rock ratio (L/R 3–30 g/g), contact time (1–3 months), temperature (25–70 °C) and oxygen concentration. To compare the effect of the concrete maturity on the argillite physico-chemical damage, the second series of batch experiments are performed with a fluid resulting from a contact with moderately degraded concrete. Experiments are carried out on powdered and compact samples in order to identify structural and geochemical modifications. Before and after contact with simplified concrete fluids, powdered solids were mainly characterised by XRD (with measurements of specific surface area and SEM observations for a selection of samples) whereas compact materials were only observed by SEM. The chemical composition of the recovered solutions was also determined for their major anions and cations with their carbon content and pH values. Interpretations are based on solid analyses and aqueous chemistry. The comparison of results obtained with powdered and compact solids is only feasible for short time experiments. Aqueous chemistry and solid analyses indicate the dissolution of pyrite, dolomite and organic carbon with the precipitation of calcite. Precipitations of zeolites and K-feldspars occur sometimes and are only evidenced by SEM analyses. Nevertheless, silicates dissolution or precipitation is unclear through XRD analyses. Experimental conditions influence widely the intensity/nature of processes and prevent the transposition of data obtained in given conditions to other ones.