Abstract

During the past 50 years, nuclear defense activities have produced large quantities of nuclear waste that now require safe and permanent disposal. The general procedure to be implemented involves the removal of cesium and strontium from the waste solutions for disposal in permanently vitrified media. This requires highly selective sorbents or ion exchangers. Further, at the high radiation doses present in the solution, organic exchangers or sequestrants are likely to decompose over time. Inorganic ion exchangers are resistant to radiation damage and can exhibit remarkably high selectivities. We have synthesized three families of tunnel-type ion exchangers. The crystal structures of these compounds as well as their protonated phases, coupled with ion exchange titrations, were determined and this information was used to develop an understanding of their ion exchange behavior. The ion exchange selectivities of these phases could be regulated by isomorphous replacement of the framework metals by larger or smaller radius metals. In the realm of layered compounds, we prepared alumina, silica, and zirconia pillared clays and sodium micas. The pillared clays yielded very high Kd values for Cs+ and were very effective in removing Cs+ from groundwaters. The sodium micas also had a high affinity for Cs+ but an even greater attraction for S42+. They also possess the property of trapping these ions permanently as the layers slowly decrease their interlayer distance as loading occurs. Sodium nonatitanate exhibited extremely high Kd values for Sr2+ in alkaline tank wastes and should be considered for removal of Sr2+ in such cases. For tank wastes containing complexing agents, we have found that adding Ca2+ to the solution releases the complexed Sr2+ which may then be removed with the CST exchanger.

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