2002 Denver Annual Meeting (October 27-30, 2002)

Paper No. 3
Presentation Time: 2:25 PM


TURNER, Andrew S. and WRONKIEWICZ, David J., Geology and Geophysics, Univ of Missouri - Rolla, 159 McNutt Hall, 1870 Miner Circle, Rolla, MO 65409-0410, asturner@umr.edu

The UO2 in spent nuclear fuel is unstable in the oxidizing conditions within the volcanic tuffs at the proposed nuclear repository at Yucca Mountain, NV. Over time, the UO2 will oxidize and corrode, releasing actinides and fission products to the surrounding environment. However, uranyl (U6+) phosphates (autunite, phurcalite, sodium autunite, etc.) are stable in such an oxidizing environment. The mobility of released radionuclides may be greatly retarded if they can be incorporated into these naturally stable phosphate phases, while their complex structures and variable chemical compositions highly favor such a process. Current tests have focused on synthesizing these phases by reacting uranium oxynitrate or UO3 with a calcium, sodium, or potassium phosphate and a base (if necessary) in a Teflon reaction vessel. Excess water is added, and the solution is heated at 90ยบC for 7, 35, or 180 days. SEM analyses have confirmed that characteristic uranium phosphate crystalline solids have formed. XRD results strongly indicate that tests using two different calcium phosphates, Ca2P2O7 and Ca10(OH)2(PO4)6, have created phosphuranylite, Ca(UO2)[(UO2)3(OH)2(PO4)2]2*12H2O (Welin, 1966), suggesting this phase is kinetically favored over other similar phases. Results utilizing sodium phosphate, NaH2(PO4)*H2O, have been inconclusive as no definitive X-ray spectrum has been observed, and results using potassium phosphate, K3PO4, are in progress. Experiments using surrogate radionuclides will be performed in order to determine whether radionuclides, such as 239Pu, 137Cs, and 99Tc, released from corroded spent nuclear fuel can become incorporated into the crystalline structure of specific uranium phosphate phases formed at the base of spent fuel containers, effectively limiting any further migration.