Determination of uranium metal concentration in irradiated fuel storage basin sludge using selective dissolution

• Published in: Journal of radioanalytical and nuclear chemistry 2014-03, Vol.299 (3), p.1871-1882
• Main Authors: Delegard, C. H., Sinkov, S. I., Chenault, J. W., Schmidt, A. J., Welsh, T. L., Pool, K. N.
• Format: Article
• Language: English
• Subjects: Basins; Building materials; Chemistry; Chemistry and Materials Science; Corrosion and anti-corrosives; Diagnostic Radiology; Dissolution; Hadrons; Heavy Ions; Inorganic Chemistry; Irradiation; Nuclear Chemistry; Nuclear Physics; Oxides; Phosphates; Phosphoric acid; Physical Chemistry; Sludge; Standard deviation; Uranium; Uranium oxides
• ISSN: 0236-5731; 1588-2780
• DOI: 10.1007/s10967-013-2884-1

Irradiated uranium metal fuel was stored underwater in the K East and K West storage basins at the US Department of Energy Hanford Site. The uranium metal under damaged cladding reacted with water to generate hydrogen gas, uranium oxides, and spalled uranium metal particles which intermingled with other particulates to form sludge. While the fuel has been removed, uranium metal in the sludge remains hazardous. An expeditious routine method to analyze 0.03 wt% uranium metal in the presence of >30 wt% total uranium was needed to support safe sludge management and processing. A selective dissolution method was designed based on the rapid uranium oxide dissolution but very low uranium metal corrosion rates in hot concentrated phosphoric acid. The uranium metal-bearing heel from the phosphoric acid step then is rinsed before the uranium metal is dissolved in hot concentrated nitric acid for analysis. Technical underpinnings of the selective dissolution method, including the influence of sludge components, were investigated to design the steps and define the reagents, quantities, concentrations, temperatures, and times within the selective dissolution analysis. Tests with simulant sludge proved the technique feasible. Tests with genuine sludge showed a 0.0028 ± 0.0037 wt% (at one standard deviation) uranium metal analytical background, a 0.011 wt% detection limit, and a 0.030 wt% quantitation limit in settled (wet) sludge. In tests using genuine K Basin sludge spiked with uranium metal at concentrations above the 0.030 wt% ± 25 % (relative) quantitation limit, uranium metal recoveries averaged 99.5 % with a relative standard deviation of 3.5 %.