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Spectral and Hydration Properties of Allophane and Imogolite

Published online by Cambridge University Press:  01 January 2024

Janice L. Bishop ,
Elizabeth B. Rampe ,
David L. Bish ,
Zaenal Abidin ,
Leslie L. Baker ,
Naoto Matsue  and
Teruo Henmi
Janice L. Bishop*
Affiliation:
Carl Sagan Center, SETI Institute and NASA-ARC, 189 Bernardo Avenue, Mountain View, CA 94043, USA
Elizabeth B. Rampe
Affiliation:
NASA-JSC, Mail Code KA, Houston, TX 77058, USA
David L. Bish
Affiliation:
Department of Geological Sciences, Indiana University, 1001 E. 10th St., Bloomington, IN 47405, USA
Zaenal Abidin
Affiliation:
Faculty of Agriculture, Ehime University, Tarumi 3-5-7, Matsuyama 790-8566, Japan Inorganic Chemistry Laboratory, Department of Chemistry, Faculty of Mathematics and Natural Science, Bogor Agricultural University, Jl. Agatis Kampus IPB Darmaga, Bogor, West of Java, 16680, Indonesia
Leslie L. Baker
Affiliation:
Department of Plant, Soil and Entomological Sciences, University of Idaho, 875 Perimeter Drive MS 2339, Moscow, ID 83844, USA
Naoto Matsue
Affiliation:
Faculty of Agriculture, Ehime University, Tarumi 3-5-7, Matsuyama 790-8566, Japan
Teruo Henmi
Affiliation:
Faculty of Agriculture, Ehime University, Tarumi 3-5-7, Matsuyama 790-8566, Japan
*
*E-mail address of corresponding author: jbishop@seti.org
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Abstract

Allophane and imogolite are common alteration products of volcanic materials. Natural and synthetic allophanes and imogolites were characterized in the present study in order to clarify the short-range order of these materials and to gain an understanding of their spectral properties. Spectral analyses included visible/near-infrared (VNIR), and infrared (IR) reflectance of particulate samples and thermal-infrared (TIR) emissivity spectra of particulate and pressed pellets. Spectral features were similar but not identical for allophane and imogolite. In the near-infrared (NIR) region, allophane spectra exhibited a doublet near 7265 and 7120 cm−1 (1.38 and 1.40 μm) due to OH2v, a broad band near 5220 cm−1 (1.92 μm) due to H2Ov+δ, and a band near 4560 cm−1 (2.19 μm) due to OHv+δ. Reflectance spectra of imogolite in this region included a doublet near 7295 and 7190 cm−1 (1.37 and 1.39 μm) due to OH2v, a broad band near 5200 cm−1 (1.92 μm) due to H2Ov+δ, and a band near 4565 cm−1 (2.19 μm) due to OHv+δ. A strong broad band was also observed near 3200–3700 cm−1 (~2.8–3.1 μm) which is a composite of OHv, H2Ov, and H2O2δ vibrations. Visible/near-infrared spectra were also collected under two relative humidity (RH) conditions. High-RH conditions resulted in increasing band strength for the H2O combination modes near 6900–6930 cm−1 (1.45 μm) and 5170–5180 cm−1 (1.93 μm) in the allophane and imogolite spectra due to increased abundances of adsorbed H2O molecules. Variation in adsorbed H2O content caused an apparent shift in the bands near 1.4 and 1.9 μm. A doublet H2Oδ vibration was observed at 1600–1670 cm−1 (~6.0–6.2 μm) and a band due to OH bending for O3SiOH was observed at ~1350–1485 cm−1 (~6.7–7.4 μm). The Si-O-Al stretching vibrations occurred near 1030 and 940 cm−1 (~9.7 and 10.6 μm) for allophane and near 1010 and 930 cm−1 (~9.9 and 10.7 μm) for imogolite. OH out-of-plane bending modes occurred near 610 cm−1 (16.4 μm) for allophane and at 595 cm−1 (16.8 μm) for imogolite. Features due to Si-O-Al bending vibrations were observed at 545, 420, and 335 cm−1 (~18, 24, and 30 μm) for allophane and at 495, 415, and 335 cm−1 (~20, 24, and 30 μm) for imogolite. The emissivity spectra were obtained from pressed pellets of the samples, which greatly enhanced the spectral contrast of the TIR absorptions. Predicted NIR bands were calculated from the mid-IR fundamental stretching and bending vibrations and compared with the measured NIR values. Controlled-RH X-ray diffraction (XRD) experiments were also performed in order to investigate changes in the mineral structure with changing RH conditions. Both allophane and imogolite exhibited decreasing low-angle XRD intensity with increasing RH, which was probably a result of interactions between H2O molecules and the curved allophane and imogolite structures.

Keywords

AllophaneEmission SpectroscopyImogoliteReflectance SpectroscopyXRD
Type
Research Article
Information
Clays and Clay Minerals , Volume 61 , Issue 1 , February 2013 , pp. 57 - 74
Copyright
Copyright © The Clay Minerals Society 2013

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References

Abidin, A. Matsue, N. and Henmi, T., 2007 Differential formation of allophane and imogolite: Experimental and molecular orbital study Journal of Computer-Aided Materials Design 14 5–18.CrossRefGoogle Scholar
Abidin, Z. Matsue, N. and Henmi, T., 2007 Nanometer-scaled chemical modification of nano-ball allophane Clays and Clay Mineral 55 443–449.CrossRefGoogle Scholar
Abidin, Z. Matsue, N. and Henmi, T., 2008 A new method for nano-tube imogolite synthesis Japanese Journal of Applied Physics 47 5079–5082.CrossRefGoogle Scholar
Abidin, Z. Matsue, N. Henmi, T., Obayashi, Y. Isobe, T. Subramanian, A. Suzuki, S. and Tanabe, S., 2009 Validity of the new method for imogolite synthesis and its genetic implication Interdisciplinary Studies on Environmental Chemistry-Environmental Research in Asia 331–341.Google Scholar
Alvarez-Ramirez, F., 2007 Ab initio simulation of the structural and electronic properties of aluminosilicate and aluminogermanate natotubes with imogolite-like structure Physical Review B 76 125–421.CrossRefGoogle Scholar
Anderson, J.H. and Wickersheim, K.A., 1964 Near infrared characterization of water and hydroxyl groups on silica surfaces Surface Science 2 252–260.CrossRefGoogle Scholar
Baker, L. and Strawn, D., 2012 Fe K-edge XAFS spectra of phyllosilicates of varying crystallinity Physics and Chemistry of Minerals 39 675–684.CrossRefGoogle Scholar
Bish, D.L. Wu, W. Carey, J.W. Costanzo, P. Giese, R.F. Earl, W. van Oss, C.J., Kodama, H. Mermut, A.R. and Torrance, J.K., 1999 Effects of steam on the surface properties of Na-smectite Clays for Our Future 569–575.Google Scholar
Bishop, J.L. Murad, E., Dyar, M.D. McCammon, C. and Schaefer, M.W., 1996 Schwertmannite on Mars? Spectroscopic analyses of schwertmannite, its relationship to other ferric minerals, and its possible presence in the surface material on Mars Mineral Spectroscopy: A tribute to Roger G. Burns St. Louis, Missouri, USA The Geochemical Society 337–358.Google Scholar
Bishop, J.L. Murad, E., Smellie, J.L. and Chapman, M.G., 2002 Spectroscopic and geochemical analyses of ferrihydrite from hydrothermal springs in Iceland and applications to Mars Volcano-Ice Interactions on Earth and Mars London Geological Society 357–370.Google Scholar
Bishop, J.L. Pieters, C.M. and Edwards, J.O., 1994 Infrared spectroscopic analyses on the nature of water in montmor-illonite Clays and Clay Minerals 42 701–715.CrossRefGoogle Scholar
Bishop, J.L. Murad, E. Madejová, J. Komadel, P. Wagner, U. Scheinost, A., Kodama, H. Mermut, A.R. and Torrance, J.K., 1999 Visible, Mössbauer and infrared spectroscopy of dioctahedral smectites: Structural analyses of the Fe-bearing smectites Sampor, SWy-1 and SWa-1 11th International Clay Conference, June, 1997 413–419.Google Scholar
Bishop, J.L. Madeová, J. Komadel, P. and Fröschl, H., 2002 The influence of structural Fe, Al and Mg on the infrared OH bands in spectra of dioctahedral smectites Clay Minerals 37 607–616.CrossRefGoogle Scholar
Bishop, J.L. Murad, E. and Dyar, M.D., 2002 The influence of octahedral and tetrahedral cation substitution on the structure of smectites and serpentines as observed through infrared spectroscopy Clay Minerals 37 617–628.CrossRefGoogle Scholar
Bishop, J.L. Lane, M.D. Dyar, M.D. and Brown, A.J., 2008 Reflectance and emission spectroscopy study of four groups of phyllosilicates: Smectites, kaolinite-serpentines, chlorites and micas Clay Minerals 43 35–54.CrossRefGoogle Scholar
Bishop, J.L. Gates, W.P. Makarewicz, H.D. McKeown, N.K. and Hiroi, T., 2011 Reflectance spectroscopy of beidellites and their importance for Mars Clays and Clay Minerals 59 376–397.CrossRefGoogle Scholar
Buurman, P. and van Reeuwijk, L.P., 1984 Proto-imogolite and the process of podzol formation: a critical note Journal of Soil Science 35 447–452.CrossRefGoogle Scholar
Chipera, S.J. Carey, J.W. Bish, D.L., Gilfrich, J.V. Noyan, I.C. Jenkins, R. Huang, T.C. Snyder, R.L. Smith, D.K. Zaitz, M.A. and Predecki, P.K., 1997 Controlled-humidity XRD analyses: Application to the study of smectite expansion/contraction Advances in X-ray Analysis New York Plenum Press 713–722.CrossRefGoogle Scholar
Christensen, P.R. and Harrison, S.T., 1993 Thermal infrared emission spectroscopy of natural surfaces: Application to desert varnish coatings on rocks Journal of Geophysical Research 98 19,819–19,834.CrossRefGoogle Scholar
Cradwick, P.D.G. Farmer, V.C. Russell, J.D. Masson, C.R. Wada, K. and Yoshinaga, N., 1972 Imogolite, a hydrated aluminium silicate of tubular structure Nature Physical Science 240 187–189.CrossRefGoogle Scholar
Creton, B. Bougeard, D. Smirnov, K.S. Guilment, J. and Poncelet, O., 2008 Structural model and computer modeling study of allophane The Journal of Physical Chemistry C 112 358–364.CrossRefGoogle Scholar
Creton, B. Bougeard, D. Smirnov, K.S. Guilment, J. and Poncelet, O., 2008 Molecular dynamics study of hydrated imogolite. 1. Vibrational dynamics of the nanotube The Journal of Physical Chemistry C 112 10013–10020.CrossRefGoogle Scholar
Demichelis, R. Noel, Y. D’Arco, P. Maschio, L. Orlando, R. and Dovesi, R., 2010 Structure and energetics of imogolite: a quantum mechanical ab initio study with B3LYP hybrid functional Journal of Materials Chemistry 20 10417–10425.CrossRefGoogle Scholar
Farmer, V.C., 1974 The layer silicates The Infrared Spectra of Minerals 4 331–363.CrossRefGoogle Scholar
Farmer, V.C. and Fraser, A.R., 1979 Synthetic Imogolite, a Tubular Hydroxyaluminium Silicate Proceedings of the VI International Clay Conference, Oxford, UK 27 547–553.Google Scholar
Farmer, V.C. Fraser, A.R. and Tait, J.M., 1977 Synthesis of imogolite: a tubular aluminum silicate polymer Journal of the Chemical Society, Clinical Communications 12 462–463.CrossRefGoogle Scholar
Farmer, V.C. Fraser, A.R. and Tait, J.M., 1979 Characterization of the chemical structures of natural and synthetic aluminosilicate gels and sols by infrared spectroscopy Geochimica et Cosmochimica Acta 43 1417–1420.CrossRefGoogle Scholar
Farmer, V.C. Adams, M.J. Fraser, A.R. and Palmieri, F., 1983 Synthetic imogolite: properties, synthesis, and possible applications Clay Minerals 18 459–472.CrossRefGoogle Scholar
Fieldes, M., 1955 Clay mineralogy of New Zealand soils, Part II: Allophane and related mineral colloids New Zealand Journal of Science and Technology 37 336–350.Google Scholar
Guimaraães, L. Enyashin, A.N. Frenzel, J. Heine, T. Duarte, H.A. and Seifert, G., 2007 Imogolite nanotubes: stability, electronic, and mechanical properties ACS Nano 1 362–368.CrossRefGoogle Scholar
Gustafsson, J.P. Karltun, E. and Bhattacharya, P., 1998.Allophane and imogolite in Swedish SoilsGoogle Scholar
Henmi, T., 1980 Effect of SiO2/Al2O3 ratio on the thermal reactions of allophane Clays and Clay Minerals 28 92–96.CrossRefGoogle Scholar
Henmi, T. Huang, P.M., Schultz, L.G. van Olphen, H. and Mumpton, F.A., 1987 Effect of phosphate on the formation of imogolite Proceedings of the International Clay Conference 1985, Denver 231–236.Google Scholar
Henmi, T. and Wada, K., 1976 Morphology and composition of allophane American Mineralogist 61 379–390.Google Scholar
Henmi, T. Tange, K. Minagawa, T. and Yoshinaga, N., 1981 Effect of SiO2/Al2O3 ratio on the thermal reactions of allophane. II. Infrared and X-ray powder diffraction data Clays and Clay Minerals 29 124–128.CrossRefGoogle Scholar
Kaufhold, S. Kaufhold, A. Jahn, R. Brito, S. Dohrmann, R. Hoffmann, R. Gliemann, H. Weidler, P. and Frechen, M., 2009 A new massive deposit of allophane raw material in Ecuador Clays and Clay Minerals 57 72–81.CrossRefGoogle Scholar
Kaufhold, S. Ufer, K. Kaufhold, A. Stucki, J.W. Anastácio, A.S. Jahn, R. and Dohrmann, R., 2010 Quantification of allophane from Ecuador Clays and Clay Minerals 58 707–716.CrossRefGoogle Scholar
Kodama, H. and Wang, C., 1989 Distribution and characterization of noncrystalline inorganic components in Spodosols and Spodosol-like soils Soil Science Society of America Journal 53 526–534.CrossRefGoogle Scholar
Konduri, S., Mukherjee, S. and Nair, S. (2006) Strain energy minimum and vibrational properties of single-walled aluminosilicate nanotubes. Physical Review B, 74, 033401.CrossRefGoogle Scholar
Lundström, U.S. Van Breemen, N. and Bain, D.C., 2000 The podzolization process. A review Geoderma 94 91–107.CrossRefGoogle Scholar
MacKenzie, K.J.D. Bowden, M.E. Brown, W.M. and Meinhold, R.H., 1989 Structure and thermal transformations of imogolite studied by 29Si and 27Al high-resolution solid-state nuclear magnetic resonance Clays and Clay Minerals 37 317–324.CrossRefGoogle Scholar
Mehra, O.P. and Jackson, M.L., 1960 Iron oxide removal from soils and clays by a dithionite-citrate system buffered with sodium bicarbonate Clays and Clay Minerals 7 317–327.CrossRefGoogle Scholar
Michalski, J.R. Kraft, M.D. Sharp, T.G. Williams, L.B. and Christensen, P.R., 2005 Mineralogical constraints on the high-silica Martian surface component observed by TES Icarus 174 161–177.CrossRefGoogle Scholar
Michalski, J.R. Kraft, M.D. Sharp, T.G. Williams, L.B. and Christensen, P.R., 2006 Emission spectroscopy of clay minerals and evidence for poorly crystalline aluminosili-cates on Mars from Thermal Emission Spectrometer data Journal of Geophysical Research 111 E03004.CrossRefGoogle Scholar
Montarges-Pelletier, E. Bogenez, S. Pelletier, M. Razafitianamaharavo, A. Ghanbaja, J. Lartiges, B. and Michot, L., 2005 Synthetic allophane-like particles: textur-al properties Colloids and Surfaces A: Physicochemical and Engineering Aspects 255 1–10.CrossRefGoogle Scholar
Morris, R.V. Lauer, H.V. Jr. Lawson, C.A. Gibson, E.K. Jr. Nace, G.A. and Stewart, C., 1985 Spectral and other physicochemical properties of submicron powders of hematite (α-Fe2O3), maghemite (γ-Fe2O3), magnetite (Fe3O4), goethite (α-FeOOH), and lepidocrocite (γ-FeOOH) Journal of Geophysical Research 90 3126–3144.CrossRefGoogle ScholarPubMed
Nagasawa, K., Sudo, T. and Shimoda, S., 1978 Weathering of volcanic ash and pyroclastic materials Clays and Clay Minerals of Japan Amsterdam Developments in Sedimentology. Kodansha, Japan and Elsevier 105–125.CrossRefGoogle Scholar
Ndayiragije, S. and Delvaux, B., 2003 Coexistence of allophane, gibbsite, kaolinite and hydroxy-Al-interlayered 2:1 clay minerals in a perudic Andosol Geoderma 117 203–214.CrossRefGoogle Scholar
Parfitt, R., 1990 Allophane in New Zealand-a review Soil Research 28 343–360.CrossRefGoogle Scholar
Parfitt, R.L., 2009 Allophane and imogolite: role in soil biogeochemical processes Clay Minerals 44 135–155.CrossRefGoogle Scholar
Parfitt, R.L. and Henmi, T., 1980 Structure of some allophanes from New Zealand Clays and Clay Minerals 28 285–294.CrossRefGoogle Scholar
Parfitt, R.L. Furkert, R.J. and Henmi, T., 1980 Identification and structure of two types of allophane from volcanic ash soils and tephra Clays and Clay Minerals 28 328–334.CrossRefGoogle Scholar
Parfitt, R.L. Childs, C.W. and Eden, D.N., 1988 Ferrihydrite and allophane in four andepts from Hawaii and implications for their classification Geoderma 41 223–241.CrossRefGoogle Scholar
Pavia, D.L. Lampman, G.M. and Kriz, G.S., 1979.Introduction to Spectroscopy: A Guide for Students of Organic ChemistryGoogle Scholar
Petit, S. Decarreau, A. Martin, F. and Buchet, R., 2004 Refined relationship between the position of the fundamental OH stretching and the first overtones for clays Physics and Chemistry of Minerals 31 585–592.CrossRefGoogle Scholar
Rampe, E.B. Kraft, M.D. Sharp, T.G. Golden, D.C. Ming, D.W. and Christensen, P.R., 2012 Allophane detection on Mars with Thermal Emission Spectrometer data and implications for regional-scale chemical weathering processes Geology 40 995–998.CrossRefGoogle Scholar
Ruff, S.W. Christensen, P.R. Barbera, P.W. and Anderson, D.L., 1997 Quantitative thermal emission spectroscopy of minerals: A technique for measurement and calibration Journal of Geophysical Research 102 14,899–14,913.CrossRefGoogle Scholar
Russell, J.D. McHardy, W.J. and Fraser, A.R., 1969 Imogolite: A unique aluminosilicate Clay Minerals 8 87–99.CrossRefGoogle Scholar
Ryskin, Y.I., Farmer, V.C., 1974 The vibrations of protons in minerals: Hydroxyl, water and ammonium The Infrared Spectra of Minerals London The Mineralogical Society 137–181.CrossRefGoogle Scholar
Saalfeld, H. and Wedde, M., 1974 Refinement of the crystal structure of gibbsite, Al(OH)3 Zeitschrift für Kristallographie 139 129–135.CrossRefGoogle Scholar
Salisbury, J.W., Pieters, C.M. and Englert, P.A.J., 1993 Mid-infrared spectroscopy: Laboratory data Remote Geochemical Analysis: Elemental and Mineralogical Composition Cambridge, UK Cambridge University Press 79–98.Google Scholar
Shimizu, H. Watanabe, T. Henmi, T. Masuda, A. and Saito, H., 1988 Studies on allophane and imogolite by high resolution solid-state Si- and A1-NMR and ESR Geochemical Journal 22 23–31.CrossRefGoogle Scholar
Shoji, S. Dahlgren, R. Nanzyo, M., Shoji, S. Nanzyo, M. and Dahlgren, R., 1993 Genesis of volcanic ash soils Volcanic Ash Soils. Genesis, Properties and Utilization Amsterdam Elsevier 37–71.CrossRefGoogle Scholar
Tamura, K. and Kawamura, K., 2001 Molecular dynamics modeling of tubular aluminum silicate: imogolite The Journal of Physical Chemistry B 106 271–278.CrossRefGoogle Scholar
Theng, B.K.G. Russell, M. Churchman, G.J. and Parfitt, R.L., 1982 Surface properties of allophane, halloysite, and imogolite Clays and Clay Minerals 30 143–149.CrossRefGoogle Scholar
van der Gaast, S.J. Wada, K. Wada, S.-I. and Kakuto, Y., 1985 Small-angle X-ray powder diffraction, morphology, and structure of allophane and imogolite Clays and Clay Minerals 33 237–243.CrossRefGoogle Scholar
Wada, K., 1967 A structural scheme of soil allophane American Mineralogist 52 690–708.Google Scholar
Wada, K., 1987 Minerals formed and mineral formation from volcanic ash by weathering Chemical Geology 60 17–28.CrossRefGoogle Scholar
Wada, K., Dixon, J.B. and Weed, S.B., 1989 Allophane and imogolite Minerals in Soil Environments Madison, Wisconsin, USA Soil Science Society of America 1051–1087.Google Scholar
Wada, S.-I. and Wada, K., 1977 Density and structure of allophane Clay Minerals 12 289–298.CrossRefGoogle Scholar
Wada, K. Henmi, T. Yoshinaga, N. and Patterson, S. H., 1972 Imogolite and allophane formed in saprolite of basalt on Maui, Hawaii Clays and Clay Minerals 20 375–380.CrossRefGoogle Scholar
Wada, S.I. Eto, A. and Wada, K., 1979 Synthetic allophane and imogolite Journal of Soil Science 30 347–355.CrossRefGoogle Scholar
Yoshinaga, N. and Aomine, S., 1962 Imogolite in some Ando soils Soil Science Plant Nutrition 8 22–29.CrossRefGoogle Scholar