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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: roy.wogelius@manchester.ac.uk
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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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References

Bargar, J.R., Reitmeyer, R. and Davis, J.A., (1999) Spectroscopic confirmation of uranium(VI)-carbonato adsorption complexes on hematite. Environmental Science & Technology, 33, 2481–2484.CrossRefGoogle Scholar
Bargar, J.R., Reitmeyer, R., Lenhart, J.J., and Davis, J.A., (2000) Characterization of U(VI)-carbonato ternary complexes on hematite: EXAFS and electrophoretic mobility measurements. Geochimica e t Cosmochimica Acta, 64, 2737–2749.CrossRefGoogle Scholar
Bondietti, E.A., and Francis, C.W., (1979) Geologic migration potentials of technetium-99 and neptunium- 237. Science, 203, 1337–1340.CrossRefGoogle ScholarPubMed
Boyanov, M.I., O’Loughlin, E.J., Roden, E.E., Fein, J.B., and Kemner, K.M., (2007) Adsorption of Fe(II) and U(VI) to carboxyl-functionalized microspheres: The influence of speciation on uranyl reduction studied by t itration and XAFS. Geochimica et Cosmochimica Acta, 71, 1898–1912.CrossRefGoogle Scholar
Braithwaite, J.W., and Molecke, M.A., (1980) Nuclear waste canister corrosion studies pertinent to geologic isolation. Nuclear and Chemical Waste Management, 1, 37–50.CrossRefGoogle Scholar
Brunauer, S., Emmett, P.H., and Teller, E. (1938) Adsorption of gases in multimolecular layers. Journal of the American Chemical Society, 60, 309–319.CrossRefGoogle Scholar
Burke, I.T., Boothman, C., Lloyd, J.R., Mortimer, R.J.G., Livens, F.R., and Morris, K. (2005) Effects of progressive anoxia on the solubility of technetium in sediments. Environmental Science & Technology, 39, 4109–4116.CrossRefGoogle ScholarPubMed
Cui, D. and Eriksen, T.E., (1996a) Reduction of pertechnetate by ferrous iron in solution: Influence of sorbed and precipitated Fe(II). Environmental Science & Technology, 30, 2259–2262.CrossRefGoogle Scholar
Cui, D. and Eriksen, T.E., (1996b) Reduction of pertechnetate in solution by heterogeneous electron transfer from Fe(II)-containing geological material. Environmental Science & Technology, 30, 2263–2269.CrossRefGoogle Scholar
Denecke, M.A., Rothe, J., Dardenne, K. and Lindqvist- Reis, P. (2003) Grazing incidence (GI) XAFS measurements of Hf(IV) and U(VI) sorption onto mineral surfaces. Physical Chemistry Chemical Physics, 5, 939–946.CrossRefGoogle Scholar
Dent, A.J., Cibin, G., Ramos, S., Smith, A.D., Scott, S.M., Varandas, L., Pearson, M.R., Krumpa, N.A., Jones, C.P., and Robbins, P.E., (2009) B18: A core XAS spectroscopy beamline for diamond. Journal of Physics: Conference Series, 190, 012039.Google Scholar
Department for Environment, Food and Rural Affairs [Defra] and the Nuclear Decommisioning Authority [NDA] (2008) Radioactive wastes in the UK: A summary of the 2007 inventory. Report Nos. Defra/ RAS/08.001 and NDA/RWMD/003. NDA, Cumbria, UK.Google Scholar
Department for Environment, Food and Rural Affairs [Defra], Department for Business, Enterprise and Regulatory Reform [BERR] and the Devolved Administration for Wales and Northern Ireland (2008) Managing radioactive waste safely – a framework for implementing geological disposal. Defra, London, UK, 100 pp.Google Scholar
Fan, D., Anitori, R.P., Tebo, B.M., Tratnyek, P.G., Lezama Pacheco, J.S., Kukkadapu, R.K., Engelhard, M.H., Bowden, M.E., Kovarik, L. and Arey, B.W., (2013) Reductive sequestration of pertechnetate (99TcO4 –) by nano zerovalent iron (NZVI) transformed by abiotic sulfide. Environmental Science & Technology, 47, 5302–5310.CrossRefGoogle Scholar
Farquhar, M.L., Wogelius, R.A., Charnock, J.M., Wincott, P., Tang, C.C., Newville, M., Eng, P.J., and Trainor, T.P., (2003) Surface oxidation of rhodonite: Structural and chemical study by surface scattering and glancing incidence XAS techniques. Mineralogical Magazine, 67, 1205–1219.CrossRefGoogle Scholar
Feiveson, H., Mian, Z., Ramana, M.V., and von Hippel, F. (2011) Managing nuclear spent fuel: Policy lessons from a 10-country study available at http:// thebulletin.org/managing-nuclear-spent-fuel-policylessons- 10-country-study. Accessed on 24 November 2013.Google Scholar
Féron, D., Crusset, D. and Gras, J.-M. (2008) Corrosion issues in nuclear waste disposal. Journal of Nuclear Materials, 379, 16–23.CrossRefGoogle Scholar
Greathouse, J.A., and Cygan, R.T., (2005) Molecular dynamics simulation of uranyl(VI) adsorption equilibria onto an external montmorillonite surface. Physical Chemistry Chemical Physics, 7, 3580–3586.CrossRefGoogle ScholarPubMed
Grenthe, I., Fuger, J., Konings, R.J.M., Lemire, R.J., Muller, A.B., Nguyen-Trung, C., and Wanner, H. (2004) Chemical thermodynamics of uranium. Organisation for Economic Co-operation and Develpoment, Nuclear Energy Agency. Data Bank, Issy-les-Moulineaux, France.Google Scholar
Hastings, J.J., Rhodes, D., Fellerman, A.S., McKendrick, D. and Dixon, C. (2007) New approaches for sludge management in the nuclear industry. Powder Technology, 174, 18–24.CrossRefGoogle Scholar
Hazan, E., Sadia, Y. and Gelbstein, Y. (2013) Characterization of AISI 4340 corrosion products using Raman spectroscopy. Corrosion Science, 74, 414–418.CrossRefGoogle Scholar
Hess, N.J., Xia, Y., Rai, D. and Conradson, S.D., (2004) Thermodynamic model for the solubility of TcO2· xH2O(am) in the aqueous Tc(IV) – Na+ – Cl– – H+ – OH– – H2O system. Journal of Solution Chemistry, 33, 199–226.CrossRefGoogle Scholar
Hiemstra, T., Venema, P. and van Riemsdijk, W.H., (1996) Intrinsic proton affinity of reactive surface groups of metal (hydr)oxides: The bond valence principle. Journal of Colloid and Interface Science, 184, 680–692.CrossRefGoogle ScholarPubMed
Hiemstra, T., Riemsdijk, W.H.V., Rossberg, A. and Ulrich, K.-U. (2009) A surface structural model for ferrihydrite II: Adsorption of uranyl and carbonate. Geochimica et Cosmochimica Acta, 73, 4437–4451.CrossRefGoogle Scholar
Hudson, E.A., Terminello, L.J., Viani, B.E., Denecke, M., Reich, T., Allen, P.G., Bucher, J.J., Shuh, D.K., and Edelstein, N.M., (1999) The structure of U6+ sorption complexes on vermiculite and hydrobiotite. Clays and Clay Minerals, 47, 439–457.CrossRefGoogle Scholar
Ilton, E.S., Pacheco, J.S.L., Bargar, J.R., Shi, Z., Liu, J., Kovarik, L., Engelhard, M.H., and Felmy, A.R., (2012) Reduction of U(VI) incorporated in the structure of hematite. Environmental Science & Technology, 46, 9428–9436.CrossRefGoogle ScholarPubMed
Istok, J.D., Senko, J.M., Krumholz, L.R., Watson, D., Bogle, M.A., Peacock, A., Chang, Y.J., and White, D.C., (2004) In situ bioreduction of technetium and uranium in a nitrate-contaminated aquifer. Environmental Science & Technology, 38, 468–475.CrossRefGoogle Scholar
Kelly, S.D., (2010) Uranium chemistry in soils and sediments. Pp. 411–466 in: Developments in soil science, Vol. 34 (S. Balwant and G. Markus, editors). Elsevier, Amsterdam.Google Scholar
Kelly, S.D., Newville, M.G., Cheng, L., Kemner, K.M., Sutton, S.R., Fenter, P., Sturchio, N.C., and Spötl, C. (2003) Uranyl incorporation in natural calcite. Environmental Science & Technology, 37, 1284–1287.CrossRefGoogle Scholar
Kelly, S.D., Rasbury, E.T., Chattopadhyay, S., Kropf, A.J., and Kemner, K.M., (2006) Evidence of a stable uranyl site in ancient organic-rich calcite. Environmental Science & Technology, 40, 2262–2268.CrossRefGoogle ScholarPubMed
Langmuir, D. (1978) Uranium solution-mineral equilibria at low-temperatures with applications to sedimentory ore-deposits. Geochimica et Cosmochimica Acta, 42, 547–569.CrossRefGoogle Scholar
Latta, D.E., Gorski, C.A., Boyanov, M.I., O’Loughlin, E.J., Kemner, K.M., and Scherer, M.M., (2011) Influence of magnetite stoichiometry on U(VI) reduction. Environmental Science & Technology, 46, 778–786.CrossRefGoogle ScholarPubMed
Latta, D.E., Boyanov, M.I., Kemner, K.M., O’Loughlin, E.J., and Scherer, M.M., (2012) Abiotic reduction of uranium by Fe(II) in soil. Applied Geochemistry, 27, 1512–1524.CrossRefGoogle Scholar
Lear, G., McBeth, J.M., Boothman, C., Gunning, D.J., Ellis, B.L., Lawson, R.S., Morris, K., Burke, I.T., Bryan, N.D., Brown, A.P., Livens, F.R., and Lloyd, J.R., (2009) Probing the biogeochemical behavior of technetium using a novel nuclear imaging approach. Environmental Science & Technology, 44, 156–162.CrossRefGoogle Scholar
Liu, J., Pearce, C.I., Qafoku, O., Arenholz, E., Heald, S.M., and Rosso, K.M., (2012) Tc(VII) reduction kinetics by titanomagnetite (Fe3–xTixO4) nanoparticles. Geochimica et Cosmochimica Acta, 92, 67–81.CrossRefGoogle Scholar
Lloyd, J.R., Sole, V.A., Van Praagh, C.V.G. and Lovley, D.R., (2000) Direct and Fe(II)-mediated reduction of technetium by Fe(III)-reducing bacteria. Applied and Environmental Microbiology, 66, 3743–3749.CrossRefGoogle ScholarPubMed
Ma, M., Zhang, Y., Guo, Z. and Gu, N. (2013) Facile synthesis of ultrathin magnetic iron oxide nanoplates by schikorr reaction. Nanoscale Research Letters, DOI: 10.1186/1556-276X-8-16.CrossRefGoogle ScholarPubMed
Macé, N., Wieland, E., Dähn, R., Tits, J. and Scheinost Andreas, C. (2013) EXAFS investigation on U(VI) immobilization in hardened cement paste: Influence of experimental conditions on speciation. Radiochimica Acta International Journal for Chemical Aspects of Nuclear Science and Technology, 101, 379–389.CrossRefGoogle Scholar
Marshall, T.A., Morris, K., Law, G.T.W., Livens, F.R., Mosselmans, J.F.W., Bots, P. and Shaw, S. (2014) Incorporation of uranium into hematite during crystallization from ferrihydrite. Environmental Science & Technology, 48, 3724–3731.CrossRefGoogle ScholarPubMed
McKenzie, H.M., Coughlin, D., Laws, F. and Stamper, A. (2011) Groundwater Annual Report 2011. Sellafield Ltd, Cumbria, UK.Google Scholar
Morris, K., Livens, F.R., Charnock, J.M., Burke, I.T., McBeth, J.M., Begg, J.D.C., Boothman, C. and Lloyd, J.R., (2008) An X-ray absorption study of the fate of technetium in reduced and reoxidised sediments and mineral phases. Applied Geochemistry, 23, 603–617.CrossRefGoogle Scholar
Morris, K., Law, G.T.W. and Bryan, N.D., (2011) Geodisposal of higher activity wastes. Pp. 129–151 in: Nuclear Power and the Environment (R.M. Harrison and R.E. Hester, editors). Issues in Environmental Science and Technology, 32. Royal Society of Chemistry, Cambridge, UK.Google Scholar
Newville, M., Ravel, B., Haskel, D., Rehr, J.J., Stern, E.A., and Yacoby, Y. (1995) Analysis of multiplescattering XAFS data using theoretical standards. Physica B: Condensed Matter, 208–209, 154–156.CrossRefGoogle Scholar
Nuclear Decommisioning Authority [NDA] (2010a) Geological Disposal: Generic Operational Safety Case main report [Report no. NDA/RWMD/020]. NDA, Didcot, UK.Google Scholar
Nuclear Decommisioning Authority [NDA] (2010b) Geological Disposal: Steps towards implementation. Executive Summary. NDA, Didcot, UK.Google Scholar
Nuclear Decommisioning Authority [NDA] (2011) The 2010 UK Radioactive Waste Inventory: Main Report. Report Nos. URN 10D/985 and NDA/ST/ STY(11)0004. NDA, Cumbria, UK.Google Scholar
O’Loughlin, E.J., Kelly, S.D., and Kemner, K.M., (2010) XAFS investigation of the interactions of U(VI) with secondary mineralization products from the bioreduction of Fe(III) oxides. Environmental Science & Technology, 44, 1656–1661.CrossRefGoogle ScholarPubMed
Ohnuki, T., Yoshida, T., Ozaki, T., Samadfam, M., Kozai, N., Yubuta, K., Mitsugashira, T., Kasama, T. and Francis, A.J., (2005) Interactions of uranium with bacteria and kaolinite clay. Chemical Geology, 220, 237–243.CrossRefGoogle Scholar
Peretyazhko, T., Zachara, J.M., Heald, S.M., Kukkadapu, R.K., Liu, C., Plymale, A.E., and Resch, C.T., (2008) Reduction of Tc(VII) by Fe(II) sorbed on Al (hydr)oxides. Environmental Science & Technology, 42, 5499–5506.CrossRefGoogle ScholarPubMed
Pointeau, I., Landesman, C., Giffaut, E. and Reiller, P. (2004) Reproducibility of the uptake of U(VI) onto degraded cement pastes and calcium silicate hydrate phases. Pp. 645. Radiochimica Acta International Journal for Chemical Aspects of Nuclear Science and Technology, 92, 645–650.Google Scholar
Quintessa, (2009) Corrosion resistance of austenitic and duplex stainless steels in environments related to UK geological disposal. A report to NDA RWMD. Report No. QRS-1384C-R1. Quintessa Ltd, Henley-on-Thames, UK.Google Scholar
Randall, J.J., and Ward, R. (1959) The preparation of some ternary oxides of the platinum metals. Journal of the American Chemical Society, 81, 2629–2631.CrossRefGoogle Scholar
Reeder, R.J., Nugent, M., Lamble, G.M., Tait, C.D., and Morris, D.E., (2000) Uranyl incorporation into calcite and aragonite: XAFS and luminescence studies. Environmental Science & Technology, 34, 638–644.CrossRefGoogle Scholar
Reeder, R.J., Nugent, M., Tait, C.D., Morris, D.E., Heald, S.M., Beck, K.M., Hess, W.P., and Lanzirotti, A. (2001) Coprecipitation of uranium(VI) with calcite: XAFS, micro-XAS, and luminescence characterization. Geochimica et Cosmochimica Acta, 65, 3491–3503.CrossRefGoogle Scholar
Russell, A.D., Emerson, S., Nelson, B.K., Erez, J. and Lea, D.W., (1994) Uranium in foraminiferal calcite as a recorder of seawater uranium concentrations. Geochimica et Cosmochimica Acta, 58, 671–681.CrossRefGoogle Scholar
Scott, T.B., Allen, G.C., Heard, P.J., and Randell, M.G., (2005) Reduction of U(VI) to U(IV) on the surface of magnetite. Geochimica et Cosmochimica Acta, 69, 5639–5646.CrossRefGoogle Scholar
Singer, D.M., Chatman, S.M., Ilton, E.S., Rosso, K.M., Banfield, J.F., and Waychunas, G.A., (2012a) Identification of simultaneous U(VI) sorption complexes and U(IV) nanoprecipitates on the magnetite (111) surface. Environmental Science & Technology, 46, 3811–3820.CrossRefGoogle Scholar
Singer, D.M., Chatman, S.M., Ilton, E.S., Rosso, K.M., Banfield, J.F., and Waychunas, G.A. (2012b) U(VI) sorption and reduction kinetics on the magnetite (111) surface. Environmental Science & Technology, 46, 3821–3830.CrossRefGoogle Scholar
Smart, N.R., Blackwood, D.J., and Werme, L. (2002) Anaerobic corrosion of carbon steel and cast iron in artificial groundwaters: Part 1 Electrochemical aspects. Corrosion, 58, 627–637.CrossRefGoogle Scholar
Thorpe, C.L., Boothman, C., Lloyd, J.R., Law, G.T.W., Bryan, N.D., Atherton, N., Livens, F.R., and Morris, K. (2014) The interactions of strontium and technetium with Fe(II) bearing biominerals: Implications for bioremediation of radioactively contaminated land. Applied Geochemistry, 40, 135–143.CrossRefGoogle Scholar
Tits, J., Geipel, G., Macé, N., Eilzer, M. and Wieland, E. (2011) Determination of uranium(VI) sorbed species in calcium silicate hydrate phases: A laser-induced luminescence spectroscopy and batch sorption study. Journal of Colloid and Interface Science, 359, 248–256.CrossRefGoogle ScholarPubMed
Topping, S. and Bruce, S. (2006) A ponderous hazard. Nuclear Engineering International, 51, 28–32 Google Scholar
van Veelen, A., Copping, R., Law, G.T.W., Smith, A.J., Bargar, J.R., Rogers, J., Shuh, D.K., and Wogelius, R.A., (2012) Uranium uptake onto magnox sludge minerals studied using EXAFS. Mineralogical Magazine, 76, 3095–3104.CrossRefGoogle Scholar
Vandergraaf, T.T., Ticknor, K.V., and George, I.M., (1984) Reactions between technetium in solution and iron-containing minerals under oxic and anoxic conditions. Pp. 25–43 in: Geochemical Behavior of Disposed Radioactive Waste (G.S. Barney, J.D., Navratil and W.W. Schulz, editors), ACS Symposium series. American Chemical Society, Washington DC.Google Scholar
Wander, M.C.F., Rosso, K.M., and Schoonen, M.A.A. (2007) Structure and charge hopping dynamics in green rust. The Journal of Physical Chemistry C, 111, 11414–11423.CrossRefGoogle Scholar
Wazne, M., Korfiatis, G.P., and Meng, X. (2003) Carbonate effects on hexavalent uranium adsorption by iron oxyhydroxide. Environmental Science & Technology, 37, 3619–3624.CrossRefGoogle ScholarPubMed
Yan-tao, L., and Bao-rong, H., (1998) Study on rust layers on steel in different marine corrosion zone. Chinese Journal of Oceanology and Limnology, 16, 231–236.CrossRefGoogle Scholar
Zhang, Q., Wang, P. and Zhang, D. (2012) Stainless steel electrochemical corrosion behaviors induced by sulphate-reducing bacteria in different aerated conditions. International Journalo f Electrochemical Science, 7, 11528–11539.Google Scholar
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