Review of the Scientific Understanding of Radioactive Waste at the U.S. DOE Hanford Site.

This Critical Review reviews the origin and chemical and rheological complexity of radioactive waste at the U.S. Department of Energy Hanford Site. The waste, stored in underground tanks, was generated via three distinct processes over decades of plutonium extraction operations. Although close records were kept of original waste disposition, tank-to-tank transfers and conditions that impede equilibrium complicate our understanding of the chemistry, phase composition, and rheology of the waste. Tank waste slurries comprise particles and aggregates from nano to micro scales, with varying densities, morphologies, heterogeneous compositions, and complicated responses to flow regimes and process conditions. Further, remnant or changing radiation fields may affect the stability and rheology of the waste. These conditions pose challenges for transport through conduits or pipes to treatment plants for vitrification. Additionally, recalcitrant boehmite degrades glass quality and the high aluminum content must be reduced prior to vitrification for the manufacture of waste glass of acceptable durability. However, caustic leaching indicates that boehmite dissolves much more slowly than predicted given surface normalized rates. Existing empirical models based on ex situ experiments and observations generally only describe material balances and have not effectively predicted process performance. Recent advances in the areas of in situ microscopy, aberration-corrected transmission electron microscopy, theoretical modeling across scales, and experimental methods for probing the physics and chemistry at mineral-fluid and mineral-mineral interfaces are being implemented to build robustly predictive physics-based models.

Evidence for dawsonite in Hanford high-level nuclear waste tanks.

Gibbsite [Al(OH)(3)] and boehmite (AlOOH) have long been assumed to be the most prevalent aluminum-bearing minerals in Hanford high-level nuclear waste sludge. The present study shows that dawsonite [NaAl(OH)(2)CO(3)] is also a common aluminum-bearing phase in tanks containing high total inorganic carbon (TIC) concentrations and (relatively) low dissolved free hydroxide concentrations. Tank samples were probed for dawsonite by X-ray Diffraction (XRD), Scanning Electron Microscopy with Energy Dispersive Spectrometry (SEM-EDS) and Polarized Light Optical Microscopy. Dawsonite was conclusively identified in four of six tanks studied. In a fifth tank (AN-102), the dawsonite identification was less conclusive because it was only observed as a Na-Al bearing phase with SEM-EDS. Four of the five tank samples with dawsonite also had solid phase Na(2)CO(3) · H(2)O. The one tank without observable dawsonite (Tank C-103) had the lowest TIC content of any of the six tanks. The amount of TIC in Tank C-103 was insufficient to convert most of the aluminum to dawsonite (Al:TIC mol ratio of 20:1). The rest of the tank samples had much lower Al:TIC ratios (between 2:1 and 0.5:1) than Tank C-103. One tank (AZ-102) initially had dawsonite, but dawsonite was not observed in samples taken 15 months after NaOH was added to the tank surface. When NaOH was added to a laboratory sample of waste from Tank AZ-102, the ratio of aluminum to TIC in solution was consistent with the dissolution of dawsonite. The presence of dawsonite in these tanks is of significance because of the large amount of OH(-) consumed by dawsonite dissolution, an effect confirmed with AZ-102 samples.