The application of carbonation treatment to cement-based wasteforms as a means to reduce the leachability of entrained undesirable substances, both radioactive and nonradioactive, has been the subject of much study over the past decade. Upon carbonation, hydrated cement phases release their water of hydration and are converted into carbonate minerals. The carbonation process has been shown to reduce the pore size distribution and permeability of the cementitious materials since portions of the original pore network become sites for precipitation of secondary carbonate minerals. As a result, the leachability of entrained contaminants can be markedly reduced. Current methods to carbonate cement-based wasteforms after they have cured rely on exposure to high pressure or supercritical CO2 pressures. In this study, a new low-pressure technique is presented. The method provides more complete carbonation than high-pressure techniques. The principle is to remove the water of reaction as it is produced, thereby maintaining an open pore network to facilitate the transfer of CO2 into the specimen. This is accomplished by conducting the reaction at near-vaccum pressures in the presence of a desiccant. The near-vacuum conditions lower the impedance of water transport from the carbonating specimen to the desiccant due to the large mean free path of the water vapor molecules. The technique was applied to a series of wasteform samples with entrained cationic and anionic waste components. Carbonation penetration depths of up to 11 mm were attained within 45 h of reaction for cylindrical wasteform samples prepared with OPC at a water/cement ratio of 0.60. A carbonation penetration depth of 15 mm was attained in a 6 d reaction of blended cement (OPC and 30% Class 'F' fly ash). In standardized leach tests, cationic waste constituents showed lower leachabilities from carbonated samples than from uncarbonated samples. Anionic waste constituents, however, showed greater leachabilities, and anion leachability increased with the degree of carbonation.

A comparison of cement wasteform carbonation under subcritical and supercritical CO2 conditions has been conducted, as well as leach tests on the carbonated products. Cement samples were prepared with water containing As, Cs, Sr, Ni and Cl, and dried under vacuum prior to exposure to CO2 gas at sub and supercritical conditions. Carbonation under supercritical conditions (50 degrees C, 1200 psi) showed similar CO2 mass uptake as subcritical carbonation (25 degrees C, 800 psi). The apparent depth of carbonation from microscopic examination, however, appeared greater with the supercritical treatment. Microscopic examination also revealed a dark intermediate zone, likely a chemical transition area, between the uncarbonated and carbonated material. Results from experiments where the initial water to cement ratio (w/c) and curing time were varied indicate that high w/c ratios and short curing times promote greater carbonation. In addition, the pore network in specimens with low w/c ratios (0.45) completely filled with water during carbonation. This caused pore water containing soluble contaminants to exude from the specimens. This does not occur at a w/c of 0.60 because the larger pore network after the drying step easily accommodates all the water produced during the reaction. No measurable arsenic or nickel were released in leach tests conducted on both carbonated and uncarbonated specimens. Calcium, cesium and strontium leachability were reduced by carbonation while the leachability of chloride and nitrate were increased with carbonation. Samples carbonated under supercritical pressure conditions showed similar leaching characteristics as samples carbonated under subcritical conditions.