Evidence for dawsonite in Hanford high-level nuclear waste tanks

Abstract

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)2CO3] 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 Na2CO3·H2O. 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.