Localized Chemistry of 99Tc in Simulated Low Activity Waste Glass

Thesis (Ph.D.), Chemistry, Washington State UniversityA priority of the United States Department of Energy (DOE) is to dispose of the nuclear waste accumulated in the underground tanks at the Hanford Nuclear Reservation in Richland, WA. Incorporation and stabilization of technetium (99Tc) from these tanks into vitrified waste forms is a concern to the waste glass community and DOE due to 99Tc’s long half-life (~2.13·10^5 y), and its high mobility in the subsurface environment under oxidizing conditions. Working in collaboration with researchers at Pacific Northwest National Laboratory (PNNL) and other national laboratories, plans were formulated to obtain first-of-a-kind chemical structure determination of poorly understood and environmentally relevant technetium compounds that relate to the chemistry of the Tc in nuclear waste glasses. Knowledge of the structure and spectral signature of these compounds aid in refining the understanding of 99Tc incorporation into and release from oxide based waste glass. In this research a first-of-its kind mechanism for the behavior of 99Tc during vitrification is presented, and the structural role of Tc(VII) and (IV) in borosilicate waste glasses is readdressed.Washington State University, Chemistry\nBy student request, this dissertation cannot be exposed to search engines and is, therefore, only accessible to Washington State University users