Effect of Iron Chloride (II) on Bentonites under Hydrothermal Gradients: A Comparative Study between Sodium Bentonite and Calcium Bentonite

Abstract

This study investigates the performance of two bentonite materials, specifically MX-80 (Na-bentonite) and FEBEX (Ca-Mg-Na-bentonite), employed as engineered barriers in deep geological disposal facilities for the isolation of high-level radioactive waste, contained in metallic canisters. Experiments conducted at the laboratory scale focused on the interaction of these bentonites with FeCl2 powder, used as a soluble iron source, to observe enhanced alteration of the bentonite. The experiments were carried out under a hydrothermal gradient. A dominant Na-Cl-SO4 saline solution was put in contact with the compacted bentonites from the top, while a constant temperature of 100 °C was maintained at the bottom using a heater in contact with the layer of FeCl2. The experimental cells were examined after six months of interaction. Various changes in the physical and chemical properties of the bentonites were observed. An increase in the water content, a reduction in the specific surface area and cation exchange capacity, changes in the distribution of aqueous species, and the formation of secondary minerals were observed. Reaction products formed at the bentonite interface with FeCl2, primarily comprising akaganeite, goethite, and hematite. The smectites showed evident structural modifications, with an enrichment in iron content, and a shift in the exchangeable ion distribution in the case of MX-80 bentonite. This work provides valuable insights into the complex interactions between bentonite barriers and materials that dissolve iron, serving as proxies for deep geological disposal environments and indicating the potential long-term behavior, taking into account higher concentrations of dissolved iron than those expected in a real repository.