DOE OSTI2017
Alkali activated alumino-silicates, often referred to as geo-polymers, are considered promising immobilization matrices for contaminants due to their high sorption capacity, durability and low leachability. For some contaminants they may prove superior to cement pastes that are conventional immobilization materials in waste management applications. However, estimating the retention capacity of some contaminants under environmental conditions that include oxidation and carbonation and may induce a valance change, is complicated. These contaminants tend to be soluble under oxidizing condition and form precipitates under reducing conditions. Thus, contaminant retention is highly dependent on the initial oxidation state at which the metal was introduced, as well as the matrix sorption ability, ability to resist oxidation and carbonation, and the contaminant leachability. Moreover, carbonation in considered one of the most important degradation mechanisms in cementitious material, causing porosity reduction and significant changes in contaminant leachability, however, geo-polymers have considerably lower Ca content relative to cements, or none, and the effect of carbonation on these pastes is less clear. Thus, contaminant release mechanisms and rates must be estimated based upon exposure to various atmospheres appropriate to waste management applications. In this study we aim to estimate the sorption capacity, and leachability of Cr from a meta-kaolin based geo-polymer, doped with Cr, as a function of its oxidation state and carbonation. Cr has a high valance range from +6 to 0 similar to Tc, and is used as its simulant in the current study. Sodium dichromate was used as an oxidized source metal material. To induce reducing conditions, ascorbic acid was added except for experimental control cases. The samples were aged under N{sub 2}, 98% N{sub 2} + 2% CO{sub 2}, CO{sub 2} deficient air and air environments under constant relative humidity. Following aging, samples were subject to equilibrium leaching as a function of pH (EPA Method 1313) and monolith mass transport rate testing (EPA Method 1315). Mass balance calculations, based on the results of a pH dependent leaching test, have shown that oxidized Cr samples lost 85-95% of their Cr content, whereas, the reduced Cr samples lost only 20% of their Cr content. On the other hand, the leachability of Si and Al is much higher in the reduced-Cr samples then in the samples with oxidized Cr, and their natural pH is up to 2.5 pH units lower than that of the oxidizing cases. Thus, we conclude that the combination of the reducing agent and the spike chemistry influence the matrix formation. Sample aging have not resulted in any significant change in the Cr-leaching behavior of the oxidizing matrices in the pH dependent leaching test, although a significant decrease in the natural pH, of 1.5 pH unit, was observed upon exposure to elevated CO{sub 2} levels (2%), probably due to the formation of Na-carbonate species. The pH and leaching behavior of the reduced Cr samples under the various aging conditions have not yielded significant variation either in their natural pH or in their leaching behavior. (authors)
12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗