Investigations Into the Nature of Alkaline Soluble, Non-Pertechnetate Technetium

This report summarizes work accomplished in fiscal year (FY) 2013, exploring the chemistry of a low-valence technetium(I) species, [Tc(CO)3(H2O)3]+, a compound of interest due to its implication in the speciation of alkaline-soluble technetium in several Hanford tank waste supernatants. Various aspects of FY 2013’s work were sponsored both by Washington River Protection Solutions and the U.S. Department of Energy’s Office of River Protection; because of this commonality, both sponsors’ work is summarized in this report. There were three tasks in this FY 2013 study. The first task involved examining the speciation of [(CO)3Tc(H2O)3]+ in alkaline solution by 99Tc nuclear magnetic resonance spectroscopy. The second task involved the purchase and installation of a microcalorimeter suitable to study the binding affinity of [(CO)3Tc(H2O)3]+ with various inorganic and organic compounds relevant to Hanford tank wastes, although the actual measure of such binding affinities is scheduled to occur in future FYs. The third task involved examining the chemical reactivity of [(CO)3Tc(H2O)3]+ as relevant to the development of a [(CO)3Tc(H2O)3]+ spectroelectrochemical sensor based on fluorescence spectroscopy