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The crystal chemistry of Al-bearing goethites: an infrared spectroscopic study

Published online by Cambridge University Press:  05 July 2018

A. J. Blanch
Affiliation:
Nanostructures and Molecular Interactions Research Group, School of Chemistry, Physics and Earth Sciences, Flinders University, Adelaide, South Australia
J. S. Quinton
Affiliation:
Nanostructures and Molecular Interactions Research Group, School of Chemistry, Physics and Earth Sciences, Flinders University, Adelaide, South Australia
C. E. Lenehan
Affiliation:
Nanostructures and Molecular Interactions Research Group, School of Chemistry, Physics and Earth Sciences, Flinders University, Adelaide, South Australia
A. Pring*
Affiliation:
Nanostructures and Molecular Interactions Research Group, School of Chemistry, Physics and Earth Sciences, Flinders University, Adelaide, South Australia Department of Mineralogy, South Australian Museum, Adelaide, South Australia
*

Abstract

Aluminium substitution into goethite, α-FeOOH, has been studied systematically by infrared spectroscopy over the frequency interval 150 to 700 cm-1. A range of synthetic compositions. (Fe1-xAlx)OOH, 0 ≤ x ≤ 0.0857, plus end-member diaspore (AlOOH) were examined. The IR spectrum of FeOOH over the range of interest can be deconvoluted into 9 peaks: 670, 633, 497, 451, 409, 396, 360, 290 and 268 cm-1. With addition of Al, the spectra become broader and the frequencies of the modes shift to higher values. An effective line width parameter Δcorr was determined by autocorrelation analysis for each spectrum and there is a significant increase in the Δcorr for compositions with >5.85 mol.% Al substitution, indicating that there is very significant structural strain associated with this solid solution at compositions where a significant number of Al sites will have an additional Al atom in the first cation coordination sphere. Trends in the values of Δcorr with composition mirrored published enthalpy of mixing values indicating that Al-goethite is metastable with respect to the goethite and diaspore end-members. The role of substitutional strain and possible partial order of Al is briefly discussed.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2008

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References

Anand, R.R., Gilkes, RJ. and Roach, G.I.D. (1991) Geochemistry and mineralogical characteristics of bauxites, Darling Range, Western Australia. Applied Geochemistry, 6, 287302.CrossRefGoogle Scholar
Anthony, J.W., Bideaux, R.A., Bladh, K. and Nichols, M.C. (1997) Handbook of Mineralogy, Volume 3 Halides, Hydroxides Oxides. Mineral data publishing, Tucson, AZ, USA, 223pp.Google Scholar
Blanch, A.J., Quinton, J.S., Lenehan, C.E., and Pring, A. (2007) Autocorrelation infrared analysis of miner-alogical samples: The influence of user controllable experimental parameters. Analytica Chimica Ada. 590, 145150.CrossRefGoogle ScholarPubMed
Boffa Ballaran, T., Carpenter, M.A., Geiger, C.A. and Koziol, A.M. (1999) Local structural heterogeneity in garnet solid solutions. Physics and Chemistry of Minerals, 26, 554569.CrossRefGoogle Scholar
Cambier, P. (1986a) Infrared study of goethites of varying crystallinity and particle size; 1. Interpretation of OH and lattice vibrations. Clay Minerals, 21, 191200.CrossRefGoogle Scholar
Cambier, P. (1986b) Infrared study of goethites of varying crystallinity and particle size; II. Crystallographic and morphological changes in series of synthetic goethites. Clay Minerals, 21, 201210.CrossRefGoogle Scholar
Cornell, R.M. and Schwertmann, U. (2006) The Iron Oxides: Structure, Properties, Reactions, Occurrences and Uses. Wiley-VCH Verlag GmbH 2nd edition, Berlin, 703 pp.Google Scholar
Demichelis, R., Noel, Y., Civalleri, B., Roetti, C, Ferrero, M. and Dovesi, R. (2007) The vibrational spectrum of a-AlOOH diaspore: An Ab Initio study with CRYSTAL code. Journal of Physical Chemistry B, 111, 93379346.CrossRefGoogle ScholarPubMed
Farmer, V.C. (editor) (1974. The Infrared Spectra of Minerals. Mineralogical Society, London, 539 pp.Google Scholar
Fazey, P.G., O'Connor, B.H. and Hammond, L.C. (1991) X-ray powder diffraction Rietveld character-ization of synthetic aluminium-subsitituted goethite. Clays and Clay Minerals, 39, 248253.CrossRefGoogle Scholar
Hazemann, J.L., Manceau, A., Sainctavit, Ph. and Malgrange, C. (1992) Structure of the a-FexAlj.x OOH solid solution. I Evidence by polarized EXAFS for an epitaxial growth of hematite like clusters in Fe-diaspore. Physics and Chemistry of Minerals, 19, 2538.Google Scholar
Hunter, B.A. (1998) Rietica - a visual Rietveld program. Commission on Powder Diffraction Newsletter, 20, 2123.Google Scholar
Majzlan, J and Navrostsky, A. (2003) Thermodynamics of the goethite-diaspore solid solution. European Journal of Mineralogy, 15, 495501.CrossRefGoogle Scholar
Meyer, H.W., Carpenter, M.A., Becerro, A.I. and Seifert, F. (2002) Hard-mode infrared spectroscopy of perovskites across the CaTiO3-SrTiO3 solid solution. American Mineralogist, 87, 12911296.CrossRefGoogle Scholar
Rietveld, H.M. (1969) Profile refinement method for nuclear and magnetic structures. Journal of Applied Crystallography, 2, 6571.CrossRefGoogle Scholar
Rodehorst, U., Carpenter, M.A., Boffa Ballaran, T. and Geiger, C.A. (2004) Local structural heterogeneity, mixing behaviour and saturation effects in the grossular-spessartine solid solutions. Physics and Chemistry of Minerals, 31, 387404.CrossRefGoogle Scholar
Ruan, H.D., Frost, R.L, Kloprogge, J.T. and Duong, L. (2002) Infrared spectroscopy of goethite dehydrox-ylation. II Effects of aluminium substitution on the behaviour of hydroxyl units. Spectrochimica Ada, Part A, 58,479—491.Google ScholarPubMed
Salje, E.K.H., Carpenter, M.A., Malcherek, T. and Boffa Ballaran, T. (2000) Autocorrelation analysis of infrared spectra from minerals. European Journal of Mineralogy, 12, 503519.CrossRefGoogle Scholar
Schulze, D.G. (1984) The influence of aluminim on iron oxides: VIII. Unit-cell dimensions of Al-substituted goethites and estimation of Al from them. Clays and Clay Minerals, 32, 3644.CrossRefGoogle Scholar
Schulze, D.G. and Schwertmann, U. (1987) The influence of aluminim on iron oxides: X. Properties of goethites synthesized in 0.3 M KOH at 25°C. Clays Minerals, 22, 8392.CrossRefGoogle Scholar
Schwertmann, U. (1984) The influence of aluminim on iron oxides: IX. Dissolution of Al-goethites in 6 M HC1. Clay Minerals, 19, 919.CrossRefGoogle Scholar
Schwertmann, U. and Carlson, L. (1994) Aluminium influence on iron oxides: XVII. Unit-cell parameters and aluminium substitution of natural goethites. Soil Science Society of America Journal, 58, 256261.CrossRefGoogle Scholar
Scheinost, A.C., Schulze, D.G. and Schwertmann, U. (1999) Diffuse reflectance spectra of Al substituted goethite: a ligand field approach. Clays and Clay Minerals, 47, 156164.CrossRefGoogle Scholar
Sileo, E.E., Ramos, A.Y., Magaz, G.E. and Blesa, M.A. (2004) Long-range vs short-range ordering in synthetic Cr-subsituted goethite. Geochimica et Cosmochimica Ada, 68, 30533063.CrossRefGoogle Scholar
Stegmann, M.C, Vivien, D. and Mazieres, C. (1973) Etude des modes de vibration infrarouge dans les oxyhydroxydes d’ aluminium boehmite et diaspore. Spectrochimica Ada, Part A, 29, 16531663.CrossRefGoogle Scholar
Szytula, A., Burewicz, A., Dimitrijevic, Z., Krasnicki, S., Rzany, H., Todorovic, J., Wanic, A. and Wolski, W. (1968) Neutron studies on α-FeOOH. Physica Status Solidi, 26, 429434.CrossRefGoogle Scholar
Tenailleau, C, Pring, A., Moussa, S.M., Liu, Y.,Withers, R.L., Tarantino, S., Zhang, M. and Carpenter, M.A. (2005) Composition induced structural phase transitions in the (Ba1-xLax)2In2O5+x (0 ≤ x ≥ 0.6) system. Journal of Solid State Chemistry, 178, 882891.CrossRefGoogle Scholar
Verdonck, L., Hoste, S., Roelandt, F.F. and van der Kelen, G.P. (1982) Normal coordinate analysis of α-FeOOH – A molecular approach. Journal of Molecular Structure, 79, 273279.CrossRefGoogle Scholar
Wolska, E. and Schwertmann, U. (1993) The mechanism of solid solution formation between goethite and diaspore. Neues Jahrbuch für Mineralogie Monatshefte, 1993, 213223.Google Scholar
Zhang, M., Wruck, B., Graeme Barber, A., Salje, E.K.H. and Carpenter, M.A. (1996) Phonon spectra of alkali feldspars: Phase transitions and solid solutions. American Mineralogist, 81, 92104.CrossRefGoogle Scholar