A Review of Geochemical Modeling for the Performance Assessment of Radioactive Waste Disposal in a Subsurface System

Abstract

Radionuclides are inorganic substances, and the solubility of inorganic substances is a major factor affecting the disposal of radioactive waste and the release of concentrations of radionuclides. The degree of solubility determines whether a nuclide source migrates to the far field of a radioactive waste disposal site. Therefore, the most effective method for retarding radionuclide migration is to reduce the radionuclide solubility in the aqueous geochemical environment of subsurface systems. In order to assess the performance of disposal facilities, thermodynamic data regarding nuclides in water–rock systems and minerals in geochemical environments are required; the results obtained from the analysis of these data can provide a strong scientific basis for maintaining safety performance to support nuclear waste management. The pH, Eh and time ranges in the environments of disposal sites cannot be controlled, in contrast to those under experimental conditions in laboratories. Using a hypothetical error mechanism for the safety assessment of disposal sites may engender incorrect assessment results. Studies have focused on radionuclide reactions in waste disposal, and have offered evidence suggesting that these reactions are mainly affected by the geochemical environment. However, studies have not examined the thermodynamics of chemical reactions or interactions between water and minerals, such as the surface complexation and adsorption of various nuclide-ion species. Simple coefficient models have usually been applied in order to obtain empirical formulas for deriving Kd to describe nuclide distributions in the solid or liquid phase in water–rock geochemical systems. Accordingly, this study reviewed previous research on the applications of geochemical models, including studies on the development of geochemical models, sources of thermodynamic databases (TDBs) and their applications in programs, the determination of the adequacy of TDBs in surface complexation models and case studies, and the selection and application of activity coefficient equations in geochemical models. In addition, the study conducted case studies and comparisons of the activity coefficients derived by different geochemical models. Three activity coefficient equations, namely the Davies, modified Debye–Hückel, and Pitzer equations, and four geochemical models, namely PHREEQC, MINEQL+, MINTEQA2, and EQ3/6, were used in the study. The results demonstrated that when the solution’s ionic strength was <0.5 m, the differences in the activity coefficients between the Davies and modified Debye–Hückel equations were <5%. The difference between the Pitzer and Davies equations, or between the Pitzer and modified Debye–Hückel equations in terms of the calculated activity coefficients was <8%. The effect of temperature on the activity coefficient slightly influenced the modeling outputs of the Davies and modified Debye–Hückel equations. In the future, the probability distribution and uncertainty of parameters of Kd and the equilibrium constant can be used in geochemical and reactive transport models to simulate the long-term safety of nuclear waste disposal sites. The findings of this study can provide a strong scientific basis for conducting safety assessments of nuclear waste disposal repositories and developing environmental management or remediation schemes to control sites marred by near-surface contamination.