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The Crystal Structure of Ianthinite, a Mixed-Valence UraniumOxide Hydrate

Published online by Cambridge University Press:  03 September 2012

Peter C. Burns ,
Robert J. Finck ,
Frank C. Hawthorne ,
Mark L. Miller  and
Rodney C. Ewing
Peter C. Burns
Affiliation:
Department of Geology, University of Illinois at Urbana-Champaign, 245 Natural History Building, 1301 West Greet Street, Urbana, IL 61801, U.S.A.
Robert J. Finck
Affiliation:
Argonne National Laboratory, Chemical Technology Division, 9700 South Cass Avenue, Argonne, IL 60439–4837, U.S.A.
Frank C. Hawthorne
Affiliation:
Department of Geological Sciences, University of Manitoba, Winnipeg, Manitoba R3T 2N2, Canada.
Mark L. Miller
Affiliation:
Department of Earth and Planetary Sciences, University of New Mexico, Albuquerque, NM 87131–1116, U.S.A.
Rodney C. Ewing
Affiliation:
Department of Earth and Planetary Sciences, University of New Mexico, Albuquerque, NM 87131–1116, U.S.A.
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Abstract

Ianthinite, [U4+2(UO2)4O6(OH)4(H2O)4](H2O)5,is the only known uranyl oxide hydrate mineral that contains U4+,and it has been proposed that ianthinite may be an important Pu4+-bearing phase during the oxidative dissolution of spent nuclear fuel. Thecrystal structure of ianthinite, orthorhombic, a 7.178(2), b 11.473(2), c. 30.39(1) Å, V 2502.7 Å3, Z = 4, spacegroup P21cn, has been solved by direct methods and refined byleast-squares methods to an R index of 9.7 % and a wR index of 12.6 % using 888 unique observed [ | F | ≥5σ | F | ] reflections. The structure contains both U6+ and U4+. The U6+ cations are present as roughly linear (U6+O2)2+ uranyl ions (Ur) that are inturn coordinated by five O2-and OH located at the equatorialpositions of pentagonal bipyramids. The U4+ cations arecoordinated by O2-, OH and H2O in a distortedoctahedral arrangement. The Urφ5 and U4+φ6 (φ: O2-, OH, H2O)polyhedra link by sharing edges to form two symmetrically distinct sheets at z z ≈ 0.0 and z ≈ 0.25 that are parallel to (001). Thesheets have the β-U3O8 sheet anion-topology. There arefive symmetrically distinct H2O groups located at z ≈ 0.125between the sheets of Uφn polyhedra, and the sheets of Uφn polyhedra are linked together only by hydrogen bonding tothe intersheet H2O groups. The crystal-chemical requirements of U4+ and Pu4+ are very similar, indicating thatextensive Pu4+ ↔ U4+ substitution can occur within thesheets of Uφn polyhedra in the structure of ianthinite.

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Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 465: Symposium II – Scienfific Basis for Nuclear Waste Management XX , 1996 , 1193
Copyright
Copyright © Materials Research Society 1997

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References

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