title: Geochemical modelling of bentonite porewater in high-level waste repositories.
abstract: The description of the geochemical properties of the bentonite backfill that serves as engineered barrier for nuclear repositories is a central issue for performance assessment since these play a large role in determining the fate of contaminants released from the waste. In this study the porewater chemistry of bentonite was assessed with a thermodynamic modelling approach that includes ion exchange, surface complexation and mineral equilibrium reactions. The focus was to identify the geochemical reactions controlling the major ion chemistry and acid-base properties and to explore parameter uncertainties specifically at high compaction degrees. First, the adequacy of the approach was tested with two distinct surface complexation models by describing recent experimental data performed at highly varying solid/liquid ratios and ionic strengths. The results indicate adequate prediction of the entire experimental data set. Second, the modelling was extended to repository conditions, taking as an example the current Swiss concept for high-level waste where the compacted bentonite backfill is surrounded by argillaceous rock. The main reactions controlling major ion chemistry were found to be calcite equilibrium and concurrent Na-Ca exchange reactions and de-protonation of functional surface groups. Third, a sensitivity analysis of the main model parameters was performed. The results thereof indicate a remarkable robustness of the model with regard to parameter uncertainties. The bentonite system is characterised by a large acid-base buffering capacity which leads to stable pH-conditions. The uncertainty in pH was found to be mainly induced by the pCO(2) of the surrounding host rock. The results of a simple diffusion-reaction model indicate only minor changes of porewater composition with time, which is primarily due to the geochemical similarities of the bentonite and the argillaceous host rock. Overall, the results show the usefulness of simple thermodynamic models to describe porewater chemistry of expandable clays although significant uncertainties with regard to the effects of swelling and physico-chemical properties of the interstitial water remain.
authors.affiliation: National Cooperative for the Disposal of Radioactive Waste (Nagra), Hardstrasse 73, CH-5430 Wettingen, Switzerland. paul.wersin@nagra.ch
authors.forename: Paul
authors.initials: P
authors.lastname: Wersin
mesh_terms: D001546:Bentonite / Q000737:chemistry*; D005544:Forecasting; D055593:Geological Phenomena; D005844:Geology; D008422:Materials Testing; D008962:Models, Theoretical; D016062:Porosity; D011850:Radioactive Waste; D013816:Thermodynamics; D018505:Waste Management
chemical_list: D011850:Radioactive Waste; D001546:Bentonite