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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

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