A key issue in performance assessment of low-level radioactive waste sites is predicting the transport and retardation of radionuclides through local soils under a variety of hydrologic and geochemical conditions. Improved transport codes should include a mechanistic model of radionuclide retardation. The authors have been investigating metal sorption (Cs{sup +}, Sr{sup 2+}, and Ba{sup 2+}) on a simple clay mineral (kaolinite) to better understand the geochemical interactions of common soil minerals with contaminated groundwaters. These studies include detailed characterizations of kaolinite surfaces, experimental adsorption measurements, surface complexation modeling, and theoretical simulations of cation sorption. The aluminol edge (010) site has been identified as the most likely site for metal sorption on kaolinite in natural solutions. Relative metal binding strengths decrease from Ba{sup 2+} to Sr{sup 2+} to Cs{sup +}, with some portion sorbed on both kaolinite edges and basal surfaces. Some Cs{sup +} also appears to be irreversibly sorbed on both sites. Molecular dynamics simulations suggest that Cs{sup +} is sorbed at aluminol (010) edge sites as an inner-sphere complex and weakly sorbed as an outer-sphere complex on (001) basal surfaces. These results provide the basis to understand and predict metal sorption onto kaolinite, and a framework to characterize sorption processes on more complex clay minerals
