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Characterization of Eu(III) co-precipitated with and adsorbed on hectorite: from macroscopic crystallites to nanoparticles

Published online by Cambridge University Press:  05 July 2018

N. Finck ,
M. Bouby ,
K. Dardenne  and
H. Geckeis
N. Finck*
Affiliation:
Institute for Nuclear Waste Disposal (INE), Karlsruhe Institute of Technology (KIT), PO Box 3640, D-76021 Karlsruhe, Germany
M. Bouby
Affiliation:
Institute for Nuclear Waste Disposal (INE), Karlsruhe Institute of Technology (KIT), PO Box 3640, D-76021 Karlsruhe, Germany
K. Dardenne
Affiliation:
Institute for Nuclear Waste Disposal (INE), Karlsruhe Institute of Technology (KIT), PO Box 3640, D-76021 Karlsruhe, Germany
H. Geckeis
Affiliation:
Institute for Nuclear Waste Disposal (INE), Karlsruhe Institute of Technology (KIT), PO Box 3640, D-76021 Karlsruhe, Germany
*
*E-mail: [email protected]
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Abstract

Hectorite was synthesized from a Eu(III)-bearing brucite precursor in a multistep procedure. In a separate experiment, Eu(III) ions were adsorbed onto hectorite in suspension. Colloids were extracted from both samples. The size distributions in the colloidal fractions were characterizedby application of the asymmetrical flow field-flow fractionation (AsFlFFF) method and the corresponding elemental compositions were obtained by ICP-MS. Extended X-ray absorption fine structure (EXAFS) spectroscopy was used to characterize the local chemical environment surrounding Eu in thebulk samples and in the colloidal fractions.

The EXAFS results show that Eu is associated with hectorite upon co-precipitation or adsorption. Results from AsFlFFF suggest that Eu is structurally associated with the colloidal fraction extracted from bulk Eu-bearing co-precipitated hectorite.The AsFlFFF data are different for the colloidal fraction containing Eu(III) adsorbed on hectorite; in this sample they are consistent with a surface retention mechanism. These small but significant differences enable surface sorbed Eu to be distinguished from co-precipitated Eu. Eu is verylikely located in a clay-like environment in the co-precipitation experiment, and it forms inner-sphere surface complexes in the adsorption experiment. The results obtained using the different experimental techniques agree, and show the benefits of using multiple methods of analysis.

Trivalent europium was used as non-radioactive chemical homologue for trivalent actinides. Similar retention mechanisms are expected for the trivalent actinides if they are co-precipitating with or adsorbing onto sheet silicates. The present study provides information which can be usefullyadded to the safety assessments required for deeply buried nuclear waste disposal sites.

Keywords

europiumhectoriteASFLFFFexafsnuclear wastegeological disposal
Type
Research Article
Information
Mineralogical Magazine , Volume 76 , Issue 7 , December 2012 , pp. 2723 - 2740
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2016

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References

Allen, P.G., Bucher, J.J., Shuh, D.K., Edelstein, N.M. and Craig, I. (2000) Coordination chemistry of trivalent lanthanide and actinide ions in dilute and concentrated chloride solutions. Inorganic Chemistry, 39, 595–601.CrossRefGoogle ScholarPubMed
Ankudinov, L.A., Ravel, B., Rehr, J.J. and Conradson, S.D. (1998) Real-space multiple-scattering calculation and interpretation of X-ray absorption near-edge structure. Physical Review B, 58, 7565–7576.CrossRefGoogle Scholar
Bouby, M., Geckeis, H., Ngo Manh, T., Yun, J.I., Dardenne, K., Schaefer, T., Walther, C. and Kim, J.I. (2004) Laser-induced breakdown detection combined with asymmetrical flow field-flow fractionation: application to iron oxi/hydroxide colloid characterization. Journal of Chromatography, A1040, 97–104.CrossRefGoogle Scholar
Bouby, M., Geckeis, H. and Geyer, F.W. (2008) Application of asymmetric flow field-flow fractionation (AsFlFFF) coupled to inductively coupled plasma mass spectrometry (ICPMS) to the quantitative characterization of natural colloids and synthetic nanoparticles. Analytical and Bioanalytical Chemistry, 392, 1447–1457.CrossRefGoogle ScholarPubMed
Bouby, M., Geckeis, H., Lützenkirchen, J., Mihai, S. and Schäfer, T. (2011) Interaction of bentonite colloids with Cs, Eu, Th and U in presence of humic acid: a flow field-flow fractionation study. Geochimica et Cosmochimica Acta, 75, 3866–3880.CrossRefGoogle Scholar
Bouby, M., Finck, N. and Geckeis, H. (2012) Flow fieldflow fractionation (AsFlFFF) coupled to sensitive detection techniques: a way to examine radionuclide interactions with nanoparticles. Mineralogical Magazine, 76, PAGINATION.CrossRefGoogle Scholar
Brandt, H., Bosbach, D., Panak, P.J. and Fanhänel, T. (2006) Structural incorporation of Cm(III) in trioctahedral smectite hectorite: a time-resolved laser fluorescence spectroscopy study. Geochimica et Cosmochimica Acta, 71, 145–154.CrossRefGoogle Scholar
Buck, E.C. and Bates, J.K. (1999) Microanalysis of colloids and suspended particles from nuclear waste glass alteration. Applied Geochemistry, 14, 635–653.CrossRefGoogle Scholar
Carrado, K.A., Thiyagarajan, P. and Song, K.A. (1997) A study of organo-hectorite clay crystallization. Clay Minerals, 32, 29–40.CrossRefGoogle Scholar
Catti, M., Ferraris, G., Hull, S. and Pavese, A. (1995) Static compression and H disorder in brucite, Mg(OH)2, to 11 GPa: a powder neutron diffraction study. Physics and Chemistry of Minerals, 22, 200–206.CrossRefGoogle Scholar
Dardenne, K., Brendebach, B., Denecke, M.A., Liu, X., Rothe, J. and Vitova, T. (2009) New developments at the INE-Beamline for actinide research at ANKA. Journal of Physics: Conference Series, 190, http:// dx.doi.org/10.1088/1742-6596.190/1/012037.CrossRefGoogle Scholar
Debure, M., Frugier, P., De Windt, L. and Gin, S. (2012) Borosilicate glass alteration driven by magnesium carbonates. Journal of Nuclear Materials, 420, 347–361.CrossRefGoogle Scholar
Dekov, V.M., Kamenov, G.D., Stummeyer, J., Thiry, M., Savelli, C., Shanks, W.C., Fortin, D., Kuzmann, E. and Vertes, A. (2007) Hydrothermal nontronite formation at Eolo Seamount (Aeolian volcanic arc, Tyrrhenian Sea). Chemical Geology, 245, 103–119.CrossRefGoogle Scholar
Finck, N., Stumpf, T., Walther, C. and Bosbach, D. (2008) TRLFS characterization of Eu(III)-doped synthetic organo-hectorite. Journal of Contaminant Hydrology, 102, 253–262.CrossRefGoogle ScholarPubMed
Finck, N., Schlegel, M.L. and Bosbach, D. (2009) Sites of Lu(III) sorbed to and coprecipitated with hectorite. Environmental Science & Technology, 43, 8807–8812.CrossRefGoogle ScholarPubMed
Gaucher, E., Blanc, P., Bardot, F., Braibant, G., Buschaert, S., Crouzet, C., Gautier, A., Girard, J.P., Jacquot, E., Lassin, A., Negrel, G., Tournassat, C., Vinsot, A. and Altmann, S. (2006) Modelling the porewater chemistry of Callovian-Oxfordian formation at the regional scale. Comptes Rendus Geoscience, 338, 917–930.CrossRefGoogle Scholar
Giddings, J.C., Yang, F.J. and Myers, M.N. (1976) Flow field-flow fractionation: a versatile new separation method. Science, 193, 1244–1245.CrossRefGoogle ScholarPubMed
Hartmann, E., Brendebach, B., Polly, R., Geckeis, H. and Stumpf, T. (2011) Characterization and quantification of Sm(III)/ and Cm(III)/clay mineral outersphere species by TRLFS in D2O and EXAFS studies. Journal of Colloid and Interface Science, 353, 562–568.CrossRefGoogle Scholar
Jollivet, P., Frugier, P., Parisot, G., Mestre, J.P., Brackx, E., Gin, S. and Schumacher, S. (2012) Effect of clayey groundwater on the dissolution rate of the simulated nuclear waste glass SON88. Journal of Nuclear Materials, 420, 508–518.CrossRefGoogle Scholar
Meunier, A. (2005) Clays. Springer, Berlin.vGoogle Scholar
Mullica, D.F., Milligan, W.O. and Beall, G.W. (1979) Crystal structure of Pr(OH)3, Eu(OH)3 and Tm(OH)3. Journal of Inorganic and Nuclear Chemistry, 41, 525–532.CrossRefGoogle Scholar
Pauling, L. (1929) The principles determining the structure of complex ionic crystals. Journal of the American Chemical Society, 51, 1010–1026.CrossRefGoogle Scholar
Philippini, V., Vercouter, T., Chausse, A. and Vitorge, P. (2008) Precipitation of ALn(CO3)2,xH2O and Dy2(CO3)3,xH2O compounds from aqueous solutions for A+ = Li+, Na+, K+, Cs+, NH4 + and Ln3+ = La3+, Nd3+, Eu3+, Dy3+. Journal of Solid State Chemistry, 181, 2143–2154.CrossRefGoogle Scholar
Ravel, B. and Newville, M. (2005) Athena, Artemis, Hephaestus: data analysis for X-ray absorption spectroscopy using IFEFFIT. Journal of Synchrotron Radiation, 12, 537–541.CrossRefGoogle ScholarPubMed
Schimpf, M., Caldwell, K. and Gilding, J.C. (2000) Field-Flow Fractionation Handbook. Wiley- Interscience, John Wiley & Sons, New York.Google Scholar
Schlegel, M.L. and Manceau, A. (2006)Evidence for the nucleation and epitaxial growth of Zn phyllosilicate on montmorillonite. Geochimica et Cosmochimica Acta, 70, 901–917.CrossRefGoogle Scholar
Seidl, W. and Breu, J. (2005) Single crystal structure refinement of tetramethylammonium hectorite. Zeitschrift für Kristallographie, 220, 169–176.Google Scholar
Severmann, S., Mills, R.A., Palmer, M.R. and Fallick, A.E. (2004) The origin of clay minerals in active and relict hydrothermal deposits. Geochimica et Cosmochimica Acta, 68, 73–88.CrossRefGoogle Scholar
Shannon, R.D. (1976) Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallographica, A32, 751–767.CrossRefGoogle Scholar
Stumpf, T., Bauer, A., Coppin, F. and Kim, J.I. (2001) Time-resolved laser fluorescence spectroscopy study on the sorption of Cm(III) onto smectite and kaolinite. Environmental Science & Technology, 35, 3691–3694.CrossRefGoogle Scholar
Teo, B. (1986) EXAFS: Basic Principles and Data Analysis. Springer Publishing, Berlin.CrossRefGoogle Scholar
Thien, B., Godon, N., Hubert, F., Angeli, F., Gin, S. and Ayral, A. (2010) Structural identification of a trioctahedral smectite formed by the aqueous alteration of a nuclear glass. Applied Clay Science, 49, 135–141.CrossRefGoogle Scholar
Utsunomiya, S., Kersting, A. and Ewing, R.C. (2009) Groundwater nanoparticles in the far-field at the Nevada test site: mechanism for radionuclide transport. Environmental Science & Technology, 43, 1293–1298.CrossRefGoogle ScholarPubMed
Wijnhoven, J.E.G.J., Koorn, J.P., Poppe, H. and Kok, W.T. (1995) Hollow-fibre flow field-flow fractionation of polystyrene sulphonates. Journal of Chromatography, A699, 119–129.CrossRefGoogle Scholar
Zwicky, H.U., Grambow, B., Magrabi, C., Aerne, E.T., Bradley, R., Barnes, B., Graber, Th., Mohos, M. and Werme, L.O. (1989) Corrosion behaviour of British Magnox waste glass in pure water. Materials Research Society Symposium Proceedings, 127, 129–136.CrossRefGoogle Scholar