Thermodynamic modeling and sensitivity analysis of porewater chemistry in compacted bentonite

Compacted bentonite is typically foreseen as the main component of the engineered barrier system of high-level radioactive waste repositories. To derive K-d values and diffusion coefficients of radionuclides for performance assessment, it is critical to be able to describe the chemistry of the pore solution and to understand how it is influenced by different factors. The present paper presents a sensitivity analysis on the influence of important parameters on porewater chemistry in compacted bentonite. The principal parameters varied were the fractions of calcite, gypsum, and NaCl dissolving from bentonite, and pCO(2): Model calculations were done with the help of a surface chemical thermodynamic model that simultaneously treats solution/mineral equilibria as well as surface complexation and ion exchange reactions at the edge and siloxane surfaces of clay minerals. Some calculations were extended to take into account electric double layer effects in the porespace. The model results show that two powerful pH buffer systems are operative in compacted bentonite: Amphoteric edge SOH sites and the carbonate buffer system. If pCO(2) is imposed externally, the resulting porewater pH is mainly controlled by the carbonate buffer. If bentonite is treated as a closed system, the buffering action of the SOH sites becomes more important. In both cases, the dissolution of calcite and gypsum from the bentonite is important. The dissolution of impurities and the ion exchange reactions have an important influence in compacted bentonite, and porewater composition is relatively independent of groundwater composition. If the development of an electric double layer in the bentonite pores is considered, our results indicate that at higher dry densities (greater than or equal to1200 kg/m(3)) the entire porespace may be occupied with (truncated) diffuse layers, leaving no space for free porewater. (C) 2004 Elsevier Ltd. All rights reserved.