Properties of selected non-pertechnetate species relevant to Hanford Tank Waste - 15019

Among radioactive constituents present in the Hanford tank waste technetium-99 (Tc) poses a multitude of problems associated with its radiotoxicity, unique and relatively poorly understood chemistry, and high mobility in the environment. Technetium is one of the most difficult contaminants to be addressed at the U.S. Department of Energy (DOE) Hanford Site because of its complex chemical behavior in tank waste and limited incorporation in the glass waste forms during mid- to high-temperature immobilization processes. The majority of Tc exists in the supernatant and salt cake fractions of both single- and double-shell tanks as pertechnetate TcO₄^- (oxidation state +7) and in the reduced forms (oxidation state < +7) collectively known as non-pertechnetate (non-TcO₄^-) species. Our research program is aimed at gaining understanding of the behavior of non-pertechnetate species in various oxidation states including such phenomena as redox speciation, hydrolysis, oligomerization, coordination of small organic ligands present in the tank supernatant, and solubility of the complex species. This paper describes our current results on the characterization and properties of the non-pertechnetate species. (authors)