Modelling coupled chemico-osmotic and advective–diffusive transport of nitrate salts in the Callovo-Oxfordian Clay

Abstract

Chemico-osmosis is a recognized phenomenon taking place in clay mineral-rich sedimentary formations and a number of questions have been raised concerning its potential effects on pressure fields in and around underground radioactive waste repositories installed in such formations. Certain radioactive waste packages contain large quantities of nitrate salts whose release might result in the presence of highly concentrated salt solutions in the disposal cells, during their resaturation after closure of the facility. This would lead to large solute concentration gradients within the formation’s porewater which could then potentially induce significant chemico-osmotic fluxes. In this paper, we assess the impact of chemico-osmotic fluxes on the water pressure during the post-closure period of a typical disposal cell for intermediate-level, long-lived bituminised radioactive waste in the Callovo-Oxfordian Clay formation. A numerical model of chemico-osmotic water flow and solute transport has been developed based on the work of Bader and Kooi (2005) [5], and including Bresler’s dependence of osmotic efficiency on concentration and compaction state [9]. Model validity has been extended to highly concentrated solutions by incorporating a concentration-dependent activity coefficient, based on the Pitzer’s equations. Results show that due to the strong dependence of the osmotic coefficient on concentration, the impact of chemico-osmosis on water flow and on the pressure field around the disposal cell is relatively low. A maximum overpressure of the order of 1MPa was obtained. No difference in the simulation results were noticed for disposal cell solutions having concentrations higher than 1M NaNO3. Differences between simulations were found to be almost entirely due to Bresler’s relationship i.e., the model of the dependence between osmotic efficiency and concentration, and only slightly on the activity coefficient correction. Questions remain regarding the appropriate function to use for describing the dependence of osmotic efficiency on salt concentration.