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Retrograde Solubilities of Source Term Phases

Published online by Cambridge University Press:  03 September 2012

William M. Murphy
William M. Murphy*
Affiliation:
Center for Nuclear Waste Regulatory Analyses, Southwest Research Institute, 6220 Culebra Road, San Antonio, TX 78228–0510USA
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Abstract

Natural analog, experimental, and thermodynamic studies indicate that the properties of secondary uranyl minerals are likely to control the source term for U and other radioéléments incorporated in these phases in the proposed Yucca Mountain repository. Thermodynamic calculations using data from the 1992 NEA data base indicate an increase in the equilibrium constant for schoepite dissolution from 103.1 to 104.8 with decreasing temperature from 100° to 25°C, i.e., retrograde solubility. Enthalpies for mineral transformation reactions that consume protons and release cations are typically negative, suggesting that solubilities of other uranyl phases such as uranophane increase more than that of schoepite with decreasing temperature. Solubilities of mineral phases associated with spent nuclear fuel will be initially relatively low under the elevated repository temperature regime. As the temperature of the repository decreases due to radioactive decay and heat dissipation, source term mineral solubilities increase. The rate of release of U and other species is controlled by a series of processes: transport of oxidants and flux of water; oxidative dissolution of spent fuel; uranyl mineral precipitation; uranyl mineral dissolution or transformation; and radionuclide transport. Decreasing diffusion and reaction rates and increasing uranyl mineral solubilities with decreasing temperature may lead to a change with time from solubility to transport or reaction rate as a source term controlling mechanism. Preservation of large quantities of uranyl minerals formed by oxidation of uraninite and radiometrie ages of secondary uranophane at the natural analog site at Peña Blanca indicate that oxidative alteration of uraninite was fast relative to transport of U away from the deposit. The successive formation of schoepite and uranophane in natural settings where uraninite has been oxidized may represent a paragenesis reflecting increasing temperature or increasing incorporation of environmental components. In contrast, diminishing temperature conditions in a repository source area could lead to the reverse sequence of mineral formation.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 465: Symposium II – Scienfific Basis for Nuclear Waste Management XX , 1996 , 713
Copyright
Copyright © Materials Research Society 1997

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References

REFERENCES

1. Murphy, W.M., and Pearcy, E.C., in Scientific Basis for Nuclear Waste Management XV, edited by Sombret, C.G. (Mater. Res. Soc. Proc. 257, Pittsburgh, PA, 1992) pp. 521–527.Google Scholar
2. Finn, P.A., Hoh, J.C., Wolf, S.F., Slater, S.A., and Bates, J.K., in Scientific Basis for Nuclear Waste Management XIX, edited by Murphy, W.M. and Knecht, D.A. (Mater. Res. Soc. Proc. 412, Pittsburgh, PA, 1996) pp. 75–81; Radiochim. Acta 74 pp. 65–71.Google Scholar
3. Grenthe, I., Fuger, J., Konings, R.J.M., Lemire, R.J., Muller, A.B., Nguyen-Trung, C., and Wanner, H., Chemical Thermodynamics of Uranium, edited by Wanner, H., and Forest, I. (Elsevier Science Publishers B.V., Amsterdam, North-Holland, 1992).Google Scholar
4. Tasker, I.R., O'Hare, P.A.G., Johnson, B.M., Johnson, G.K., Cordfunke, E.H.P., Can. J. Chem. 66 (1988) pp. 620–625.10.1139/v88-106Google Scholar
5. Nguyen, S.N., Silva, R.J., Weed, H.C., and Andrews, J.E. Jr., J. Chem. Thermo. 24 (1992) pp. 259–276.10.1016/S0021-9614(05)80155-7Google Scholar
6. Casas, I., Bruno, J., Cera, E., Finch, R.J., and Ewing, R.C., in Kinetic and Thermodynamic Studies of Uranium Minerals Assessment of the Long-Term Evolution of Spent Nuclear Fuel, (Swedish Nuclear Fuel and Waste Management Company, Technical Report 94–16, Stockholm, Sweden, 1994) p. 73.Google Scholar
7. Moll, H., Geipel, G., Matz, W., Bernhard, G., and Nitsche, H., Radiochim. Acta 74 pp. 3–7 (1996).10.1524/ract.1996.74.special-issue.3Google Scholar
8. Holland, H.D. and Brush, L.H., in Proceedings of the Conference on High-Level Radioactive Solid Waste Forms, edited by Casey, L.A., Nuclear Regulatory Commission, NUREG/CP-005, 1979, p. 597–615.Google Scholar
9. Finch, R.J., Hawthorne, F.C., and Ewing, R.C., in Scientific Basis for Nuclear Waste Management XIX, edited by Murphy, W.M. and Knecht, D.A. (Mater. Res. Soc. Proc. 412, Pittsburgh, PA, 1996) pp. 361–368.Google Scholar
10. Weast, R.C., CRC Handbook of Chemistry and Physics, edited by Astle, M.J., and Beyer, W.H., (CRC Press Inc., Boca Raton, Florida, 1988).Google Scholar
11. Based on the EQ3/6 data base data0.com.R2, Lawrence Livermore National Laboratory (1995).Google Scholar
12. Frondel, C., Systematic Mineralogy of Uranium and Thorium, (U.S. Geological Survey Bulletin 1064. Washington, DC: U.S. Government Printing Office, 1958).Google Scholar
13. Gray, W.J., Leider, H.R., and Steward, S.A., J. Nuc. Mater. 190 (1992) pp. 46–52.10.1016/0022-3115(92)90074-UGoogle Scholar
14. Pearcy, E.C., Prikryl, J.D., Murphy, W.M., and Leslie, B.W., App. Geochem. 9 (1994) pp. 713–732.10.1016/0883-2927(94)90030-2Google Scholar
15. Pickett, D.A., Prikryl, J.D., Murphy, W.M., and Pearcy, E.C., Submitted to App. Geochem. (1996).Google Scholar
16. Broxton, D.E., Bish, D.L., and Warren, R.G., Clay Clay Min. 35 (1987) pp. 89–110.10.1346/CCMN.1987.0350202Google Scholar
17. Einziger, R.E., Thomas, L.E., Buchanan, H.C., and Stout, R.B., J. Nuc. Mater. 190 (1992) pp. 53–60.10.1016/0022-3115(92)90075-VGoogle Scholar
18. Wronkiewicz, D.J., Bates, J.K., Gerding, T.J., Veleckis, E., and Tani, B.S., J. Nuc. Mater. 190 (1992) pp. 107–127.10.1016/0022-3115(92)90081-UGoogle Scholar
19. Wilson, C.N., in Scientific Basis for Nuclear Waste Management XIV, edited by Abrajano, T.A. Jr., (Mater. Res. Soc. Proc 212, Pittsburgh, PA, 1991) pp. 197–204.Google Scholar
20. Cachoir, Ch., Guittet, M.J., Gallien, J.-P., and Trocellier, P., Radiochim. Acta 74 (1996) pp. 59–63.10.1524/ract.1996.74.special-issue.59Google Scholar
21. Taylor, R., Lemire, R.J., and Wood, D.D., inHigh Level Radioactive Waste Management, (Amer. Nuc. Soc., La Grange Park, IL, 1992) pp. 1, 442–1, 448.Google Scholar