Solubility measurements of the uranyl oxide hydrate phases metaschoepite, compreignacite, Na–compreignacite, becquerelite, and clarkeite

Gorman-Lewis, Drew; Fein, Jeremy B.; Burns, Peter C.; Szymanowski, Jennifer E.S.; Converse, Jenalee

doi:10.1016/j.jct.2008.02.006

Solubility measurements of the uranyl oxide hydrate phases metaschoepite, compreignacite, Na–compreignacite, becquerelite, and clarkeite

Journal Article · Sun Jun 01 00:00:00 EDT 2008 · Journal of Chemical Thermodynamics

DOI:https://doi.org/10.1016/j.jct.2008.02.006· OSTI ID:1064430

Gorman-Lewis, Drew ^[1]; Fein, Jeremy B.; Burns, Peter C.; Szymanowski, Jennifer E.S.; Converse, Jenalee

University of Notre Dame

The mobility of uranium under oxidizing conditions can only be modeled if the thermodynamic stabilities of the secondary uranyl minerals are known. Toward this end, we synthesized metaschoepite (UO(3)(H(2)O)(2)), becquerelite (Ca(UO(2))(6)O(4)(OH)(6)(H(2)O)(8)), compreignacite (K(2)(UO(2))(6)O(4)(OH)(6)(H(2)O)(7)), sodium compreignacite (Na(2)(UO(2))(6)O(4)(OH)(6)(H(2)O)(7)), and clarkeite (Na(UO(2))O(OH)) and performed solubility measurements from both undersaturation and supersaturation under controlled-pH conditions. The solubility measurements rigorously constrain the values of the solubility products for these synthetic phases, and consequently the standard-state Gibbs free energies of formation of the phases. The calculated Ig solubility product values (IgK(sp)), with associated 1 sigma uncertainties, for metaschoepite, becquerelite, compreignacite, sodium compreignacite, and clarkeite are (5.6 -0.2/+0.1), (40.5 -1.4/+0.2), (35.8 -0.5/+0.3), (39.4 -1.1/+0.7), and (9.4 -0.9/+0.6), respectively. The standard-state Gibbs free energies of formation, with their 2 sigma uncertainties, for these same phases are (-1632.2 +/- 7.4) kJ . mol(-1), (-10305.6 +/- 26.5) kJ +/- mol(-1), (-10107.3 +/- 21.8) kJ . mol(-1), (-10045.6 +/-24.5) kJ . mol(-1), and (-1635.1 +/- 23.4) kJ . mol(-1), respectively. Combining our data with previously measured. standard-state enthalpies of formation for metaschoepite, becquerelite, sodium compreignacite, and clarkeite yields calculated standard-state entropies of formation, with associated 2 sigma uncertainties, of (-532.5 +/- 8.1) J . mol(-1) . K(-1), (-3634.5 +/- 29.7) J . mol(-1) . K(-1), (-2987.6 +/- 28.5) J . mol(-1) . K(-1), and (-300.5 +/- 23.9) J - mol(-1) - K(-1), respectively. The measurements and associated calculated thermodynamic properties from this study not only describe the stability and solubility at T=298 K, but also can be used in predictions of uranium mobility through extrapolation of these properties to temperatures and pressures of geologic and environmental interest.

Research Organization:: University of Notre Dame, IN (United States)

Sponsoring Organization:: USDOE; USDOE SC Office of Biological and Environmental Research (SC-23)

DOE Contract Number:: FG02-07ER64395

OSTI ID:: 1064430

Report Number(s):: DOE/ER/64395-1

Journal Information:: Journal of Chemical Thermodynamics, Journal Name: Journal of Chemical Thermodynamics Journal Issue: 6 Vol. 40; ISSN 0021-9614

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

References (31)

The solubility of (UO2)3(PO4)2 · 4H2O(s) and the formation of U(VI) phosphate complexes: Their influence in uranium speciation in natural waters Sanding, Amaia; Bruno, Jordi Geochimica et Cosmochimica Acta, Vol. 56, Issue 12 https://doi.org/10.1016/0016-7037(92)90256-I	journal	December 1992
Incorporation mechanisms of actinide elements into the structures of U6+ phases formed during the oxidation of spent nuclear fuel Burns, Peter C.; Ewing, Rodney C.; Miller, Mark L. Journal of Nuclear Materials, Vol. 245, Issue 1 https://doi.org/10.1016/S0022-3115(97)00006-8	journal	May 1997
Theoretical prediction of the thermodynamic behavior of aqueous electrolytes by high pressures and temperatures; IV, Calculation of activity coefficients, osmotic coefficients, and apparent molal and standard and relative partial molal properties to 600 degrees C and 5kb Helgeson, H. C.; Kirkham, D. H.; Flowers, G. C. American Journal of Science, Vol. 281, Issue 10 https://doi.org/10.2475/ajs.281.10.1249	journal	December 1981
The Solubility of Amorphous and Crystalline Schoepite in Neutral to Alkaline Aqueous Solutions Bruno, Jordi; Sandino, Amaia MRS Proceedings, Vol. 127 https://doi.org/10.1557/PROC-127-871	journal	January 1988
Thermodynamic properties of soddyite from solubility and calorimetry measurements Gorman-Lewis, Drew; Mazeina, Lena; Fein, Jeremy B. The Journal of Chemical Thermodynamics, Vol. 39, Issue 4 https://doi.org/10.1016/j.jct.2006.09.005	journal	April 2007
Neptunium(V) Partitioning to Uranium(VI) Oxide and Peroxide Solids Douglas, Matthew; Clark, Sue B.; Friese, Judah I. Environmental Science & Technology, Vol. 39, Issue 11 https://doi.org/10.1021/es0405169	journal	June 2005
Dissolution of Uranyl-Oxide-Hydroxy-Hydrate Minerals. ii. Becquerelite Schindler, M.; Hawthorne, F. C.; Burns, P. C. The Canadian Mineralogist, Vol. 44, Issue 5 https://doi.org/10.2113/gscanmin.44.5.1207	journal	October 2006
Thermodynamics of uranyl minerals: Enthalpies of formation of uranyl oxide hydrates Kubatko, K. -A.; Helean, K.; Navrotsky, A. American Mineralogist, Vol. 91, Issue 4 https://doi.org/10.2138/am.2006.1856	journal	April 2006
Review of uranyl mineral solubility measurements Gorman-Lewis, Drew; Burns, Peter C.; Fein, Jeremy B. The Journal of Chemical Thermodynamics, Vol. 40, Issue 3 https://doi.org/10.1016/j.jct.2007.12.004	journal	March 2008
Uranium release and secondary phase formation during unsaturated testing of UO2 at 90°C Wronkiewicz, David J.; Bates, John K.; Gerding, Thomas J. Journal of Nuclear Materials, Vol. 190 https://doi.org/10.1016/0022-3115(92)90081-U	journal	August 1992
Neptunium incorporation into uranyl compounds that form as alteration products of spent nuclear fuel: Implications for geologic repository performance Burns, Peter C.; Deely, Kathryn M.; Skanthakumar, Suntharalingam Radiochimica Acta, Vol. 92, Issue 3 https://doi.org/10.1524/ract.92.3.151.30491	journal	January 2004
A Bond-Valence Approach to the Uranyl-Oxide Hydroxy-Hydrate Minerals: Chemical Composition and Occurrence Schindler, M.; Hawthorne, F. C. The Canadian Mineralogist, Vol. 42, Issue 6 https://doi.org/10.2113/gscanmin.42.6.1601	journal	December 2004
The Gibbs free energies and enthalpies of formation of U (super 6+) phases; an empirical method of prediction Chen, Fanrong; Ewing, Rodney C.; Clark, Sue B. American Mineralogist, Vol. 84, Issue 4 https://doi.org/10.2138/am-1999-0418	journal	April 1999
Behaviour of U(VI) solids under conditions of natural aquatic systems Meinrath, G.; Kimura, T. Inorganica Chimica Acta, Vol. 204, Issue 1 https://doi.org/10.1016/S0020-1693(00)88116-5	journal	February 1993
Alteration of uraninite from the Nopal I deposit, Pen˜a Blanca District, Chihuahua, Mexico, compared to degradation of spent nuclear fuel in the proposed U.S. high-level nuclear waste repository at Yucca Mountain, Nevada Pearcy, English C.; Prikryl, James D.; Murphy, William M. Applied Geochemistry, Vol. 9, Issue 6 https://doi.org/10.1016/0883-2927(94)90030-2	journal	November 1994
The corrosion of uraninite under oxidizing conditions Finch, Robert J.; Ewing, Rodney C. Journal of Nuclear Materials, Vol. 190 https://doi.org/10.1016/0022-3115(92)90083-W	journal	August 1992
Ten-year results from unsaturated drip tests with UO2 at 90°C: implications for the corrosion of spent nuclear fuel Wronkiewicz, David J.; Bates, John K.; Wolf, Stephen F. Journal of Nuclear Materials, Vol. 238, Issue 1 https://doi.org/10.1016/S0022-3115(96)00383-2	journal	October 1996
Thermodynamics of the U(VI)-Ca²⁺-Cl⁻-OH⁻-H₂O system: Solubility product of becquerelite Rai, Dhanpat; Felmy, Andrew R.; Hess, Nancy J. Radiochimica Acta, Vol. 90, Issue 9-11 https://doi.org/10.1524/ract.2002.90.9-11_2002.495	journal	September 2002
A common source of error in pH measurements Illingworth, J. A. Biochemical Journal, Vol. 195, Issue 1 https://doi.org/10.1042/bj1950259	journal	April 1981
Solid-Aqueous Phase Equilibria of Uranium(VI) under Ambient Conditions Meinrath, G.; Kato, Y.; Kimura, T. ract, Vol. 75, Issue 3 https://doi.org/10.1524/ract.1996.75.3.159	journal	December 1996
Characterization and dissolution behavior of a becquerelite from Shinkolobwe, Zaire Casas, Ignasi; Bruno, Jordi; Cera, Esther Geochimica et Cosmochimica Acta, Vol. 61, Issue 18 https://doi.org/10.1016/S0016-7037(97)00195-6	journal	September 1997
U6+ Minerals and Inorganic Compounds: Insights into an Expanded Structural Hierarchy of Crystal Structures Burns, P. C. The Canadian Mineralogist, Vol. 43, Issue 6 https://doi.org/10.2113/gscanmin.43.6.1839	journal	December 2005
Influence of Dissolved Sodium and Cesium on Uranyl Oxide Hydrate Solubility Giammar, Daniel E.; Hering, Janet G. Environmental Science & Technology, Vol. 38, Issue 1 https://doi.org/10.1021/es0345672	journal	January 2004
Oxidative Corrosion of Spent uo ₂ Fuel in Vapor and Dripping Groundwater at 90°C Finch, Robert J.; Buck, Edgar C.; Finn, Patricia A. MRS Proceedings, Vol. 556 https://doi.org/10.1557/PROC-556-431	journal	January 1999
Equilibrium and kinetic aspects of soddyite dissolution and secondary phase precipitation in aqueous suspension Giammar, Daniel E.; Hering, Janet G. Geochimica et Cosmochimica Acta, Vol. 66, Issue 18 https://doi.org/10.1016/S0016-7037(02)00927-4	journal	September 2002
Neptunium incorporation in sodium-substituted metaschoepite Klingensmith, A. L.; Deely, K. M.; Kinman, W. S. American Mineralogist, Vol. 92, Issue 4 https://doi.org/10.2138/am.2007.2350	journal	April 2007
Solubility Equilibria in the U(VI)-Ca-K-Cl-H₂O System: Transformation of Schoepite into Becquerelite and Compreignacite Sandino, M. C. Amaia; Grambow, Bernd ract, Vol. 66-67, Issue Supplement https://doi.org/10.1524/ract.1994.6667.special-issue.37	journal	December 1994
Solubility Products and Complex Formation Equilibria in the Systems Uranyl Hydroxide and Uranyl Carbonate at 25°C and I = 0.1 M Kramer-Schnabel, U.; Bischoff, H.; Xi, R. H. ract, Vol. 56, Issue 4 https://doi.org/10.1524/ract.1992.56.4.183	journal	April 1992
Microscale characterization of uranium(VI) silicate solids and associated neptunium(V) Douglas, Matthew; Clark, Sue B.; Friese, Judah I. Radiochimica Acta, Vol. 93, Issue 5 https://doi.org/10.1524/ract.93.5.265.64281	journal	January 2005
Transformation of schoepite into the uranyl oxide hydrates: Becquerelite, billietite and wölsendorfite Vochten, R.; Van Haverbeke, L. Mineralogy and Petrology, Vol. 43, Issue 1 https://doi.org/10.1007/BF01164222	journal	August 1990
Weathering of Natural Uranyl Oxide Hydrates: Schoepite Polytypes and Dehydration Effects Finch, Robert J.; Miller, Mark L.; Ewing, Rodney C. ract, Vol. 58-59, Issue 2 https://doi.org/10.1524/ract.1992.5859.2.433	journal	June 1992

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uranyl oxide hydrate solubility

Solubility measurements of the uranyl oxide hydrate phases metaschoepite, compreignacite, Na–compreignacite, becquerelite, and clarkeite

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