One of the methods being considered for safely disposing of Category 3 low-level radioactive wastes is to encase the waste in concrete. Such concrete encasement would contain and isolate the waste packages from the hydrologic environment and would act as an intrusion barrier. The current plan for waste isolation consists of stacking low-level waste packages on a trench floor, surrounding the stacks with reinforced steel, and encasing these packages in concrete. These concrete-encased waste stacks are expected to vary in size with maximum dimensions of 6.4 m long, 2.7 m wide, and 4 m high. The waste stacks are expected to have a surrounding minimum thickness of 15 cm of concrete encasement. These concrete-encased waste packages are expected to withstand environmental exposure (solar radiation, temperature variations, and precipitation) until an interim soil cover or permanent closure cover is installed, and to remain largely intact thereafter. Any failure of concrete encasement may result in water intrusion and consequent mobilization of radionuclides from the waste packages. The mobilized radionuclides may escape from the encased concrete by mass flow and/or diffusion and move into the surrounding subsurface environment. Therefore, it is necessary to assess the performance of the concrete encasement structure and the ability of the surrounding soil to retard radionuclide migration. The retardation factors for radionuclides contained in the waste packages can be determined from measurements of diffusion coefficients for these contaminants through concrete and fill material. Some of the mobilization scenarios include (1) potential leaching of waste form before permanent closure cover is installed; (2) after the cover installation, long-term diffusion of radionuclides from concrete waste form into surrounding fill material; (3) diffusion of radionuclides from contaminated soils into adjoining concrete encasement and clean fill material. Additionally, the rate of diffusion of radionuclides may be affected by the formation of structural cracks in concrete, the carbonation of the buried waste form, and any potential effect of metallic iron (in the form of rebars) on the mobility of radionuclides. The radionuclides iodine-129 (129I), technetium-99 (99Tc), and uranium-238 (238U) are identified as long-term dose contributors in Category 3 waste (Mann et al. 2001; Wood et al. 1995). Because of their anionic nature in aqueous solutions, 129I, 99Tc, and carbonate-complexed 238U may readily leach into the subsurface environment (Serne et al. 1989, 1992a, b, 1993, and 1995). The leachability and/or diffusion of radionuclide species must be measured to assess the long-term performance of waste grouts when contacted with vadose-zone pore water or groundwater. Although significant research has been conducted on the design and performance of cementitious waste forms, the current protocol conducted to assess radionuclide stability within these waste forms has been limited to the Toxicity Characteristic Leaching Procedure, Method 1311 Federal Registry (EPA 1992) and ANSI/ANS-16.1 leach test (ANSI 1986). These tests evaluate the performance under water-saturated conditions and do not evaluate the performance of cementitious waste forms within the context of waste repositories which are located within water-deficient vadose zones. Moreover, these tests assess only the diffusion of radionuclides from concrete waste forms and neglect evaluating the mechanisms of retention, stability of the waste form, and formation of secondary phases during weathering, which may serve as long-term secondary hosts for immobilization of radionuclides. The results of recent investigations conducted under arid and semi-arid conditions (Al-Khayat et al. 2002; Garrabrants et al. 2002; Garrabrants and Kosson 2003; Garrabrants et al. 2004; Gervais et al. 2004; Sanchez et al. 2002; Sanchez et al. 2003) provide valuable information suggesting structural and chemical changes to concrete waste forms which may affect contaminant containment and waste form performance. However, continued research is necessitated by the need to understand: the mechanism of contaminant release; the significance of contaminant release pathways; how waste form performance is affected by the full range of environmental conditions within the disposal facility; the process of waste form aging under conditions that are representative of processes occurring in response to changing environmental conditions within the disposal facility; the effect of waste form aging on chemical, physical, and radiological properties, and the associated impact on contaminant release. Recent reviews conducted by the National Academies of Science recognized the efficacy of cementitious materials for waste isolation, but further noted the significant shortcomings in our current understanding and testing protocol for evaluating the performance of various formulations.