In the safety assessment of radioactive waste disposal, it is critical to understand the porewater chemistry in compacted bentonite in order to predict long-term migration behavior of radionuclides in the engineered barrier. This study estimates the activity coefficients of dissolved ions in the porewater of compacted bentonite from the concentrations of ions at which CaCO3 precipitation occurred. Solutions containing CaCl2 and NaHCO3 were introduced under electrical potential gradient from the opposite sides of the compacted Na-bentonite packed at the dry density of 1.0 kg/dm 3. After the electromigration, the spatial distribution of ions along the compacted bentonite sample was determined. Sequential extraction method was developed to distinctly determine the concentrations of free ions in the porewater and in solid phase in bentonite. The results show that the exchangeable Na + ions were progressively replaced by the incoming Ca 2+ ions, and the compacted bentonite sample can be divided into three zones: Ca-, Ca-/Na-, and Na-bentonite zones. Precipitates of CaCO3 were observed both in Ca-and Ca/Na-bentonite zones. The experimentally determined activity coefficients were at least smaller by a factor of three compared to the theoretical approximation calculated using PHREEQC code assuming dilute-solution conditions with no electrostatic interactions between ions and bentonite surface.
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