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Uranium and technetium interactions with wüstite [Fe1–xO] and portlandite [Ca(OH)2] surfaces under geological disposal facility conditions

Published online by Cambridge University Press:  05 July 2018

A. Van Veelen ,
O. Preedy ,
J. Qi ,
G. T. W. Law ,
K. Morris ,
J. F. W. Mosselmans ,
M. P. Ryan ,
N. D. M. Evans  and
R. A. Wogelius
A. Van Veelen
Affiliation:
University of Manchester, Williamson Research Centre for Molecular Environmental Science, School of Earth, Atmospheric and Environmental Sciences, Oxford Road, Manchester M13 9PL, UK
O. Preedy
Affiliation:
Department of Chemistry, Loughborough University, Loughborough LE11 3TU, UK
J. Qi
Affiliation:
Imperial College London, Department of Materials, Exhibition Road, London SW7 2AZ, UK
G. T. W. Law
Affiliation:
University of Manchester, School of Chemistry, Oxford Road, Manchester M13 9PL, UK
K. Morris
Affiliation:
University of Manchester, Research Centre for Radwaste and Decommissioning and Williamson Research Centre for Molecular Environmental Science, School of Earth, Atmospheric and Environmental Sciences, Oxford Road, Manchester M13 9PL, UK
J. F. W. Mosselmans
Affiliation:
Diamond Light Source, Harwell Science and Innovation Campus, Didcot OX11 0DE, UK
M. P. Ryan
Affiliation:
Imperial College London, Department of Materials, Exhibition Road, London SW7 2AZ, UK
N. D. M. Evans
Affiliation:
Department of Chemistry, Loughborough University, Loughborough LE11 3TU, UK
R. A. Wogelius*
Affiliation:
University of Manchester, Williamson Research Centre for Molecular Environmental Science, School of Earth, Atmospheric and Environmental Sciences, Oxford Road, Manchester M13 9PL, UK
*
* E-mail: [email protected]
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Abstract

Iron oxides resulting from the corrosion of large quantities of steel that are planned to be installed throughout a deep geological disposal facility (GDF) are expected to be one of the key surfaces of interest for controlling radionuclide behaviour under disposal conditions. Over the lengthy timescales associated with a GDF, the system is expected to become anoxic so that reduced Fe(II) phases will dominate. Batch experiments have therefore been completed in order to investigate how a model reduced Fe-oxide surface (wüstite, Fe1–xO) alters as a function of exposure to aqueous solutions with compositions representative of conditions expected within a GDF. Additional experiments were performed to constrain the effect that highly alkaline solutions (up to pH 13) have on the adsorption behaviour of the uranyl (UO22+) ion onto the surfaces of both wüstite and portlandite [Ca(OH)2; representative of the expected cementitious phases]. Surface co-ordination chemistry and speciation were determined by ex situ X-ray absorption spectroscopy measurements (both X-ray absorption near-edge structure analysis (XANES) and extended X-ray absorption fine structure analysis (EXAFS)). Diffraction, elemental analysis and XANES showed that the bulk solid composition and Fe oxidation state remained relatively unaltered over the time frame of these experiments (120 h), although under alkaline conditions possible surface hydroxylation is observed, due presumably to the formation of surface hydroxyl complexes. The surface morphology, however, is altered significantly with a large degree of roughening and an observed decrease in the average particle size. Reduction of U(VI) to U(IV) occurs during adsorption in almost all cases and this is interpreted to indicate that wüstite may be an effective reductant of U during surface adsorption. This work also shows that increasing the carbonate concentration in reactant solutions dramatically decreases the adsorption coefficients for U on both wüstite and portlandite, consistent with U speciation and surface reactivity determined in other studies. Finally, the EXAFS results include new details about exactly how U bonds to this metal oxide surface.

Keywords

Uraniumtechnetiumiron oxideswüstiteportlanditeradionuclide behaviourgeological disposal
Type
Research Article
Information
Mineralogical Magazine , Volume 78 , Issue 5 , October 2014 , pp. 1097 - 1113
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2014

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