Hostname: page-component-cd9895bd7-gvvz8 Total loading time: 0 Render date: 2024-12-18T19:51:40.125Z Has data issue: false hasContentIssue false

Degradation of phosphatic waste forms incorporating long-lived radioactive isotopes

Published online by Cambridge University Press:  05 July 2018

D. Read*
Affiliation:
Enterpris Ltd., University of Reading, Whiteknights, Reading, Berks RG6 6AB, UK
C. T. Williams
Affiliation:
Department of Mineralogy, Natural History Museum, Cromwell Road, London SW7 5BD, UK
*

Abstract

This paper provides a brief perspective on synthetic, phosphate-based waste forms for high level radioactive waste (HLW). Evidence in support of their long-term stability is then discussed by reference to the degradation of natural monazites with emphasis on the fate of released uranium, thorium and the rare earths (REE). It is apparent that the REE can be mobilized and fractionated at temperatures anticipated in a HLW repository (∼200°C). This provides an indication of the likely fate of the trivalent actinides (Am(III), Cm(III)) if incorporated in similar matrices. Thorium, though released on alteration of monazite, tends to re-concentrate locally in secondary, microcrystalline phases. In relative terms, U is readily removed from monazites. Although it can be re-concentrated in alteration products, the potential exists for substantial loss of U to groundwater. The findings of this research have important implications for the performance of radioactive waste disposal systems where there is a clear need for improved chemical data to describe the precipitation-dissolution of phosphate phases. It is concluded that monazite-like ceramics designed for the containment of HLW will retain tetravalent actinides but may release uranium in response to natural degradative processes.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2001

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Andreoli, M.A.G., Smith, C.B., Watkeys, M., Moore, J.M., Ashwal, L.D. and Hart, R.J. (1994) The geology of the Steenkampskraal monazite deposit, South Africa: Implications for REE-Th-Cu mineralization in charnockite-granulite terranes. Econ. Geol., 89, 994–1016.CrossRefGoogle Scholar
Bénard, P., Louer, D., Dacheux, N., Brandel, V. and Genet, M. (1994) U(UO2)(PO4)2, a new mixed-valence uranium orthophosphate: Ab Initio structure determination from powder diffraction data and optical and X-ray photoelectron spectra. Chem. Mater., 6, 1049–58.CrossRefGoogle Scholar
Bénard, P., Brandel, V., Dacheux, N., Jaulmes, S., Launay, S., Lindecker, C., Genet, M., Louer, D. and Quarton, M. (1996) Th4(PO4)4P2O7, a new thorium phosphate: Synthesis, characterization and structure determination. Chem. Mater., 8, 181–8.CrossRefGoogle Scholar
Boatner, L.A. and Sales, B.C. (1988) Monazite. Pp. 495564 in: Radioactive Waste Forms for the Future (Lutze, W. and Ewing, R.C., editors). Elsevier, North Holland.Google Scholar
Brandel, V., Dacheux, N. and Genet, M. (1996) Re-examination of uranium (IV) phosphate chemistry. J. Solid State Chem., 121, 467–72.CrossRefGoogle Scholar
Brookins, D.G. (1990) Radionuclide behaviour at the Oklo nuclear reactor, Gabon. Waste Manag., 10, 285–96.CrossRefGoogle Scholar
Chakhmouradian, A.R. and Mitchell, R.H. (1998) Lueshite, pyrochlore and monazite- (Ce) from apatite-dolomite carbonatite, Lesnaya Varaka complex, Kola Peninsula, Russia. Mineral. Mag., 62, 769–82.CrossRefGoogle Scholar
Dacheux, N., Podor, R., Chassigneux, B., Brandel, V. and Genet, M. (1998) Actinides immobilization in new matrices based on solid solutions: Th4−xMIV x(PO4)4P2O7, (MIV=238U, 239Pu). J. Alloys Compounds, 271-273, 236–9.CrossRefGoogle Scholar
Dall’aglio, M., Gragnani, N. and Locardi, E. (1974) Geochemical factors controlling the formation of the secondary minerals of uranium. In Formation of Uranium Ore Deposits. IAEA, Vienna.Google Scholar
Dongarra, G. and Langmuir, D. (1980) The stability of UO2OH+ and UO2(HPO4)2 2− complexes at 25°C. Geochim. Cosmochim. Acta, 44, 1747–51.CrossRefGoogle Scholar
Donnot, M., Guiges, J., Lulzac, Y., Magnien, A., Parfenoff, A. and Picot, P. (1973) Un nouveau type de gisement d’europium: la monazite grise à europium en nodules dans les schists paléozoique de Bretagne. Miner. Deposita, 8, 718.CrossRefGoogle Scholar
Eyal, Y. and Olander, D.R. (1990) Leaching of uranium and thorium from monazite: I. Initial leaching. Geochim. Cosmochim. Acta, 54, 1867–77.CrossRefGoogle Scholar
Falck, W.E., Read, D. and Thomas, J.B. (1996) CHEMVAL2 thermodynamic database. CEC Report EUR 16897.Google Scholar
Fleischer, M. and Altschuler, Z.S. (1969) The relationship of the rare earth composition of minerals to geological environment. Geochim. Cosmochim. Acta, 33, 725–32.CrossRefGoogle Scholar
Forster, H.J. and Harlov, D.E. (1999) Monazite-(Ce)- huttonite solid solutions in granulite-facies metabasites from the Ivrea-Verbano Zone, Italy. Mineral. Mag., 63, 587–94.CrossRefGoogle Scholar
Glendinning, J.E. (1996) Factors influencing the mobility of uranium, thorium and rare earth elements at the Steenkampskraal monazite mine, North Western Cape. Unpublished MSc Dissertation, Department of Geological Sciences, University of Cape Town.Google Scholar
Grenthe, I., Fuger, J., Lemire, R.J., Muller, A.B., Nguyen-Trung, C. and Wanner, H. (1992) Chemical Thermodynamics of Uranium. Chemical Thermodynamics Series, 1. Elsevier, North Holland.Google Scholar
Hsi, C.-K.D. and Langmuir, D. (1985) Adsorption of uranyl onto ferric oxyhydroxides: Application of the surface complexation site-binding model. Geochim. Cosmochim. Acta, 49, 1931–41.Google Scholar
Lanzirotti, A. and Hanson, G.N. (1996) Geochronology and geochemistry of multiple generations of monazite from the Wepawaug Schist, Connecticut, USA: Implications for monazite stability in metamorphic rocks. Contrib. Mineral. Petrol., 125, 332–40.CrossRefGoogle Scholar
Marivoet, J., Volckaert, G., Sneyers, A. and Wibin, J. (1996) First performance assessment of the disposal of spent fuel in clay layers. CEC Report EUR 16752.Google Scholar
Meldrum, A., Boatner, L.A. and Ewing, R.C. (2000) A comparison of radiation effects in crystalline ABO4-type phosphates and silicates. Mineral. Mag., 64, 185–94.CrossRefGoogle Scholar
Mordberg, L.E., Stanley, C.J. and Germann, K. (2001) Mineralogy and geochemistry of trace elements in bauxites: the Devonian Schugorsk deposit, Russia. Mineral. Mag., 65, 81101.CrossRefGoogle Scholar
Moskvin, A.I., Shelyakina, A.M. and Perminov, P.S. (1967) Solubility product of uranyl phosphate and the composition and dissociation constants of uranyl phosphato-complexes. Russ. J. Inorg. Chem., 12, 1756–60.Google Scholar
Murakami, T., Ohnuki, T., Isobe, H. and Sato, T. (1997) Mobility of uranium during weathering. Amer. Mineral., 82, 888–99.CrossRefGoogle Scholar
Olander, D.R. and Eyal, Y. (1990 a) Leaching of uranium and thorium from monazite: II. Elemental leaching. Geochim. Cosmochim. Acta, 54, 1879–87.CrossRefGoogle Scholar
Olander, D.R. and Eyal, Y. (1990 b) Leaching of uranium and thorium from monazite: III. Leaching of radiogenic daughters. Geochim. Cosmochim. Acta, 54, 1889–96.CrossRefGoogle Scholar
Pearcy, E., Prikryl, J., Murphy, W. and Leslie, B. (1994) Alteration of uraninite from the Nopal I deposit, Peña Blanca district, Chihuahua, Mexico compared to degradation of spent nuclear fuel in the proposed US high level nuclear waste repository at Yucca Mountain, Nevada. Appl. Geochem., 9, 713–32.CrossRefGoogle Scholar
Poitrasson, F., Chenery, S. and Bland, D.J. (1996) Contrasted monazite hydrothermal alteration mechanisms and their geochemical implications. Earth Planet. Sci. Lett., 145, 7996.CrossRefGoogle Scholar
POSIVA (1999) Application for a decision in principle regarding a final disposal facility for spent nuclear fuel. Application to the Finnish Council of State, May 1999.Google Scholar
Read, D., Cooper, D.C. and McArthur, J.M. (1987) The composition and distribution of nodular monazite in the Lower Palaeozoic rocks of Great Britain. Mineral. Mag., 51, 271–80.CrossRefGoogle Scholar
Read, D., Thomas, J.B., Bennett, D., Swanton, S. and Ivanovich, M. (1994) Transport of actinide-bearing colloids through siliceous matrices. Radiochim. Acta, 66/67, 683–9.Google Scholar
Read, D., Blomqvist, R., Rasilainen, K. and Ruskeeniemi, T. (1999 a) Uranium migration in glaciated terrain: Implications of the Palmottu study, Southern Finland. Proc. NEA Geotrap Conf., Carlsbad, New Mexico. Google Scholar
Read, D., Jarvis, N. and Andreoli, M. (1999 b) Thorium, uranium and rare earth element behaviour at the Steenkampskraal monazite mine, South Africa. Proc. 8th CEC Natural Analogue Meeting, Strasbourg. Google Scholar
Read, D., Jarvis, N., Williams, C.T., Knoper, M. and Andreoli, M. (2001) The degradation of monazite: Implications for the mobility of rare earth and actinide elements during low temperature alteration. Manuscript submitted to Eur. J. Mineral. CrossRefGoogle Scholar
Sales, B.C. and Boatner, L.A. (1988) Lead- iron phosphate glass. Pp. 193231 in: Radioactive Waste Forms for the Future (Lutze, W. and Ewing, R.C., editors). Elsevier, North Holland.Google Scholar
Silva, R.J., Bidoglio, G., Rand, M.H., Robouch, P.B., Wanner, H. and Puigdomenech, I. (1995) Chemical Thermodynamics of Americium. Chemical Thermodynamics Series, 2. Elsevier, North Holland.Google Scholar
Vochten, R. and Deliens, M. (1980) Transformation of curite into meta-autunite: Paragenesis and electro-kinetic properties. Phys. Chem. Miner., 6, 129–43.CrossRefGoogle Scholar
Vochten, R., Huybrechts, W., Remaut, G. and Deliens, M. (1979) Formation of meta-torbernite starting from curite: Crystallographic data and electrokinetic properties. Phys. Chem. Miner., 4, 281–90.CrossRefGoogle Scholar
Waite, T.D., Davis, J.A., Payne, T.E., Waychunas, G.A. and Xu, N. (1994) Uranium (VI) adsorption to ferrihydrite: Application of a surface complexation model. Geochim. Cosmochim. Acta, 58, 5465–78.CrossRefGoogle Scholar
Wood, S.A. and Ricketts, A. (2000) Allanite-(Ce) from the Eocene Casto Granite, Idaho: Response to hydrothermal alteration. Canad. Mineral., 38, 81100 CrossRefGoogle Scholar