Adsorption of Ba and 226Ra on illite: A comparative experimental and modelling study

Abstract

Illite, smectite and illite/smectite mixed layers are major phases in various argillaceous rock formations foreseen as potential host rocks for the deep geological disposal of high-level radioactive waste and are important sorbents for cationic radionuclides potentially released in the repository. 226Ra is a critical radionuclide in the safety analysis and an important source of radioactivity in technically enhanced naturally occurring radioactive materials. A comprehensive study was carried out on the adsorption of Ba and Ra on purified homoionic Na-illite (Illite du Puy) over a wide range of experimental conditions (pH, concentration, ionic strength) allowing for the development of a quasi-mechanistic Ba/Ra adsorption model for illite. Ba adsorption isotherms obtained at fixed ionic strength and pH exhibit a non-linear behaviour in the Ba equilibrium concentration range between ∼10−7 and ∼10−2 M. The pH dependent adsorption of trace 226Ra and Ba was investigated at different ionic strengths and evidenced a more pronounced adsorption of 226Ra than Ba on illite. Finally, a competition experiment of trace 226Ra in the presence of increasing Ba concentrations showed an unexpected 226Ra adsorption behaviour which was not observed for montmorillonite in earlier studies. This large set of experimental data could be successfully modelled by Ba/226Ra exchange reactions against Na, together with selectivity coefficients, on two different site types, namely planar sites and high affinity sites. The modelling of the pH dependent adsorption of Ba and 226Ra at high ionic strength and high pH required an additional surface complexation reaction. Two additional exchange sites had to be introduced to quantitatively describe the 226Ra uptake on illite in the 226Ra/Ba competition experiment. The nature of these sites, however, remains unclear. The implementation of the 226Ra adsorption model into predictive transport modelling codes is of key importance for the safety analysis of deep geological disposal of radioactive waste.