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The Structure of U6+ Sorption Complexes on Vermiculite and Hydrobiotite

Published online by Cambridge University Press:  28 February 2024

Eric A. Hudson ,
Louis J. Terminello ,
Brian E. Viani ,
Melissa Denecke ,
Tobias Reich ,
Patrick G. Allen ,
Jerome J. Bucher ,
David K. Shuh  and
Norman M. Edelstein
Eric A. Hudson*
Affiliation:
Glenn T. Seaborg Institute for Transactinium Science, Lawrence Livermore National Laboratory, L-231, P.O. Box 808, Livermore, California 94551, USA
Louis J. Terminello
Affiliation:
Glenn T. Seaborg Institute for Transactinium Science, Lawrence Livermore National Laboratory, L-231, P.O. Box 808, Livermore, California 94551, USA
Brian E. Viani
Affiliation:
Earth and Environmental Sciences Directorate, Lawrence Livermore National Laboratory, L-219, P.O. Box 808, Livermore, California 94551, USA
Melissa Denecke
Affiliation:
Institut für Radiochemie, Forschungszentrum Rossendorf, Postfach 510119, D-01314 Dresden, Germany
Tobias Reich
Affiliation:
Institut für Radiochemie, Forschungszentrum Rossendorf, Postfach 510119, D-01314 Dresden, Germany
Patrick G. Allen
Affiliation:
Glenn T. Seaborg Institute for Transactinium Science, Lawrence Livermore National Laboratory, L-231, P.O. Box 808, Livermore, California 94551, USA Lawrence Berkeley National Laboratory, MS 70A-1150, 1 Cyclotron Rd., Berkeley, California 94720, USA
Jerome J. Bucher
Affiliation:
Lawrence Berkeley National Laboratory, MS 70A-1150, 1 Cyclotron Rd., Berkeley, California 94720, USA
David K. Shuh
Affiliation:
Lawrence Berkeley National Laboratory, MS 70A-1150, 1 Cyclotron Rd., Berkeley, California 94720, USA
Norman M. Edelstein
Affiliation:
Lawrence Berkeley National Laboratory, MS 70A-1150, 1 Cyclotron Rd., Berkeley, California 94720, USA
*
†Present address: Lam Research Corp., CA-3, 4650 Cushing Pkwy., Fremont, California 94538, USA.
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Abstract

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The sorption of the uranyl oxo-cation (UO22+)at different types of binding sites on layer silicate mineral surfaces was investigated. Well-characterized samples of vermiculite and hydrobiotite were exposed to aqueous uranyl under conditions designed to promote surface sorption either at fixed charge ionexchange sites or at amphoteric surface hydroxyl sites. The local structure of uranium in the sorption samples was directly measured using uranium L3-edge extended X-ray absorption fine structure (EXAFS). Polarized L1- and L3-edge X-ray absorption near-edge structure (XANES) measurements were used to characterize the orientation of uranyl groups in layered samples. X-ray diffraction (XRD) measurements of interlayer spacings were used to assess the effects of ion-exchange and dehydration upon the mineral structure. The most significant findings are: (1) Under conditions which greatly favor ion-exchange sorption mechanisms, uranyl retains a symmetric local structure suggestive of an outer-sphere complex, with a preferred orientation of the uranyl axis parallel to the mineral layers; (2) Upon dehydration, the ionexchange complexes adopt a less symmetric structure, consistent with an inner-sphere complex, with less pronounced orientation of the uranyl axis; and (3) For conditions which favor sorption at surface hydroxyl sites, uranyl has a highly distorted equatorial shell, indicative of stronger equatorial ligation, and the detection of a neighboring U atom suggests the formation of surface precipitates and/or oligomeric complexes.

Keywords

Cation ExchangeEXAFSSorptionSurface ComplexUraniumUranylVermiculiteXANESXRD
Type
Research Article
Information
Clays and Clay Minerals , Volume 47 , Issue 4 , August 1999 , pp. 439 - 457
Copyright
Copyright © 1999, The Clay Minerals Society

References

Allen, P.G. Bucher, J.J. Clark, D.L. Edelstein, N.M. Ekberg, S.A. Gohdes, J.W. Hudson, E.A. Kaltsoyannis, N. Lukens, W.W. Neu, M.P. Palmer, P.D. Reich, T. Shuh, D.K. Tait, C.D. and Zwick, B.D., 1995 Multinuclear NMR, Raman, EXAFS, and x-ray diffraction studies of uranyl carbonate complexes in near-neutral aqueous solutions Inorganic Chemistry 34 4797–4807 10.1021/ic00123a013.CrossRefGoogle Scholar
Allen, P.G. Shuh, D.K. Bucher, J.J. Edelstein, N.M. Reich, T. Denecke, M.A. and Nitsche, H., 1996 EXAFS determination of uranium structures: The uranyl ion complexed with tartaric, citric, and malic acids Inorganic Chemistry 35 784–787 10.1021/ic9508536.CrossRefGoogle Scholar
Allen, P.G. Shuh, D.K. Bucher, J.J. Edelstein, N.M. Palmer, C.E.A. Silva, R.J. Nguyen, S.N. Marquez, L.N. and Hudson, E.A., 1996 EXAFS determination of uranium structures: Schoepite and other U(VI) oxide precipitates Radiochimica Acta 75 47–53 10.1524/ract.1996.75.1.47.CrossRefGoogle Scholar
Baes, C.F. Jr. and Mesmer, R.E., 1976 The Hydrolysis of Cations New York Wiley.Google Scholar
Bayliss, P. Erd, D.C. Mrose, M.E. Sabina, A.P. and Smith, D.K., 1986 Mineral Powder Diffraction File Data Book Swarthmore, Pennsylvania, USA International Center for Diffraction Data.Google Scholar
Brindley, G.W. Zalba, P.E. and Bethke, C.M., 1983 Hydrobiotite, a regular 1:1 interstratification of biotite and vermiculite layers American Mineralogist 68 420–425.Google Scholar
Brown, G.E. Jr., Hochella, M.E. Jr. and White, A.F., 1990 Spectroscopic studies of chemisorption reaction mechanisms at oxide-water Interfaces Reviews in Mineralogy, Volume 23, Mineral-Water Interface Geochemistry Washington, D.C Mineral Society of America 309–363 10.1515/9781501509131-012.CrossRefGoogle Scholar
Bucher, J.J. Edelstein, N.M. Osborne, K.P. Shuh, D.K. Madden, N. Luke, P. Pehl, D. Cork, C. Malone, D. and Allen, P.G., 1996 A multi-channel Ge detector system for fluorescence x-ray absorption spectroscopy Reviews of Scientific Instruments 67 1–4 10.1063/1.1146862.CrossRefGoogle Scholar
Chisholm-Brause, C. Conradson, S.D. Buscher, C.T. Eller, P.G. and Morris, D.E., 1994 Speciation of uranyl sorbed at multiple binding sites on montmorillonite Geochimica et Cosmochimica Acta 58 3625–3631 10.1016/0016-7037(94)90154-6.CrossRefGoogle Scholar
Dent, A.J. Ramsay, J.D.E. and Swanton, S.W., 1992 An EXAFS study of uranyl ion in solution and sorbed onto silica and montmorillonite clay colloids Journal of Colloid and Interface Science 150 45–60 10.1016/0021-9797(92)90267-P.CrossRefGoogle Scholar
Farges, E. Ponader, C.W. Calas, G. and Brown, G.E. Jr., 1992 Structural environments of incompatible elements in silicate glass/melt systems: II. UIV, UV, and UVI Geochimica et Cosmochimica Acta 56 4205–4220 10.1016/0016-7037(92)90261-G.CrossRefGoogle Scholar
Giaquinta, D.M. Soderholm, L. Yuchs, S.E. and Wasserman, S.R., 1997 The speciation of uranium in a smectite clay: Evidence for catalysed uranyl reduction Radiochimica Acta 76 113–121 10.1524/ract.1997.76.3.113.CrossRefGoogle Scholar
Grenthe, I. Fuger, J. Konings, R.J.M. Lemire, R.J. Muller, A.B. Nguyen-Trung, C. and Wanner, H., 1992 Chemical Thermodynamics of Uranium: Nuclear Energy Agency, Chemical Thermodynamics, Volume I New York North-Holland Elsevier Science.Google Scholar
Hudson, E.A. Rehr, J.J. and Bucher, J.J., 1995 Multiplescattering calculations of the uranium L3-edge x-ray-absorption near-edge structure Physical Review B 52 13815–13826 10.1103/PhysRevB.52.13815.CrossRefGoogle ScholarPubMed
Hudson, E.A. Allen, P.G. Terminello, L.J. Denecke, M. and Reich, T., 1996 Polarized x-ray absorption spectra of the uranyl ion: Comparison of theory and experiment Physical Review B 54 156–165 10.1103/PhysRevB.54.156.CrossRefGoogle Scholar
Lemire, R.J. and Tremaine, P.R., 1980 Uranium and plutonium equilibra in aqueous solutions to 200°C Journal of Chemical and Engineering Data 25 361–370 10.1021/je60087a026.CrossRefGoogle Scholar
MacEwan, D.M.C. Wilson, M.J., Brindley, G.W. and Brown, G., 1980 Interlayer and intercalation complexes of clay minerals Crystal Structures of Clay Minerals and Their X-ray Identification London Mineralogical Society 197–248.CrossRefGoogle Scholar
Nguyen, S.N. Silva, R.J. Weed, H.C. and Andrews, J.E. Jr., 1992 Standard Gibbs free energies of formation at the temperature 303.15 K of four uranyl silicates: Soddyite, uranophane, sodium boltwoodite, and sodium weeksite Journal of Chemical Thermodynamics 24 359–376 10.1016/S0021-9614(05)80155-7.CrossRefGoogle Scholar
Petiau, J. Calas, G. Petitmaire, D. Bianconi, A. Benfatto, M. and Marcelli, A., 1986 Delocalized versus localized unoccupied 5f states and the uranium site structure in uranium oxides and glasses probed by x-ray-absorption nearedge structure Physical Review B 34 7350–7631 10.1103/PhysRevB.34.7350.CrossRefGoogle ScholarPubMed
Prikryl, J.D. Pabalan, R.T. Turner, D.R. and Leslie, B.W., 1994 Uranium sorption on α-alumina: Effects of pH and surface-area/solution-volume ratio Radiochimica Acta 291–296.CrossRefGoogle Scholar
Rehr, J.J. de Mustre Leon, J. Zabinsky, S.I. and Albers, R.C., 1991 Theoretical X-ray Absorption Fine Structure Standards Journal of the American Chemical Society 113 5135–5140 10.1021/ja00014a001.CrossRefGoogle Scholar
Reich, T. Moll, H. Denecke, M.A. Geipel, G. Bernhard, G. Nitsche, H. Allen, P.G. Bucher, J.J. Kaltsoyannis, N. Edelstein, N.M. and Shuh, D.K., 1996 Characterization of hydrous uranyl silicate by EXAFS Radiochimica Acta 74 219–223 10.1524/ract.1996.74.special-issue.219.CrossRefGoogle Scholar
Sawhney, B.L., 1967 Interstratification in vermiculite Clays and Clay Minerals 15 75–84 10.1346/CCMN.1967.0150109.CrossRefGoogle Scholar
Sposito, G., 1984 The Surface Chemistry of Soils New York Oxford University Press.Google Scholar
Suib, S.L. Tanguay, J.E. and Occelli, M.L., 1986 Comparison of the photochemical and photophysical properties of clays, pillared clays, and zeolites Journal of the American Chemical Society 108 6972–6977 10.1021/ja00282a022.CrossRefGoogle Scholar
Taylor, J.C., 1971 The structure of the α form of uranyl hydroxide Acta Crystallographica B 27 1088–1091 10.1107/S056774087100356X.CrossRefGoogle Scholar
Templeton, D.H. and Templeton, L.K., 1982 X-ray dichroism and polarized anomalous scattering of the uranyl ion Acta Crystallographica A 38 62–67 10.1107/S0567739482000114.CrossRefGoogle Scholar
Tsunashima, A. Brindley, G.W. and Bastovanov, M., 1981 Adsorption of uranium from solutions by montmorillonite: Compositions and properties of uranyl montmorillonites Clays and Clay Minerals 29 10–16 10.1346/CCMN.1981.0290102.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 Geochimica et Cosmochimica Acta 58 5465–5478 10.1016/0016-7037(94)90243-7.CrossRefGoogle Scholar