Hostname: page-component-848d4c4894-pjpqr Total loading time: 0 Render date: 2024-06-26T06:40:10.011Z Has data issue: false hasContentIssue false
  • English
  • Français

XAFS Study of Fe-Substituted Allophane and Imogolite

Published online by Cambridge University Press:  01 January 2024

Leslie L. Baker ,
Ryan D. Nickerson  and
Daniel G. Strawn
Leslie L. Baker*
Affiliation:
Division of Soil and Land Resources, University of Idaho, Moscow, ID 83844-3022, USA
Ryan D. Nickerson
Affiliation:
Division of Soil and Land Resources, University of Idaho, Moscow, ID 83844-3022, USA
Daniel G. Strawn
Affiliation:
Division of Soil and Land Resources, University of Idaho, Moscow, ID 83844-3022, USA
*
*E-mail address of corresponding author: lbaker@uidaho.edu
Get access Rights & Permissions [Opens in a new window]

Abstract

The nano-aluminosilicate mineral allophane is common in soils formed from parent materials containing volcanic ash and often contains Fe. Due to its lack of long-range order, the structure of allophane is still not completely understood. In the present study, Fe K-edge X-ray absorption fine structure (XAFS) was used to examine Fe-containing natural and synthetic allophane and imogolite samples. Results indicated that Fe substitutes for octahedrally coordinated Al in allophane, and that Fe exhibits a clustered distribution within the octahedral sheet. Iron adsorbed on allophane surfaces is characterized by spectral features distinct from those of isomorphically substituted Fe and of ferrihydrite. Fe adsorbed on the allophane surfaces probably exists as small polynuclear complexes exhibiting Fe-Fe edge sharing, similar to poorly crystalline Fe oxyhydroxides. The XAFS spectra of natural allophane and imogolite indicate that the Fe in the minerals is a combination of isomorphically substituted and surface-adsorbed Fe. In the synthetic Fe-substituted allophanes, the Fe XAFS spectra did not vary with the Al:Si ratio. Theoretical fits of the extended XAFS (EXAFS) spectra suggest that local atomic structure around octahedral Fe in allophanes is more similar to Fe in a smectite-like structure than to a published theoretical nanoball structure.

Keywords

AllophaneFe K-edge XAFSImogolite
Type
Article
Information
Clays and Clay Minerals , Volume 62 , Issue 1 , February 2014 , pp. 20 - 34
Copyright
Copyright © Clay Minerals Society 2014

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

Ajiboye, B. Akinremi, O.O. and Jürgensen, A., 2007 Experimental validation of quantitative XANES analysis for phosphorus speciation Soil Science Society of America Journal 71 1288–1291.CrossRefGoogle Scholar
Baker, L.L. and Strawn, D.G., 2012 Fe K-edge XAFS spectra of phyllosilicates of varying crystallinity Physics and Chemistry of Minerals 39 675–684.CrossRefGoogle Scholar
Baker, L.L. Strawn, D.G. Vaughan, K.L. and McDaniel, P.A., 2010 XAS study of Fe mineralogy in a chronosequence of soil clays formed in basaltic cinders Clays and Clay Minerals 58 772–782.CrossRefGoogle Scholar
Barron, P. Wilson, M. Campbell, A.S. and Frost, R., 1982 Detection of imogolite in soils using solid state 29Si NMR Nature 299 616–618.CrossRefGoogle Scholar
Chen, L.X. Liu, T. Thurnauer, M.C. Csencsits, R. and Rajh, T., 2002 Fe2O3 nanoparticle structures investigated by Xray absorption near-edge structure, surface modifications, and model calculations The Journal of Physical Chemistry B 106 8539–8546.CrossRefGoogle Scholar
Childs, C.W. Parfitt, R.L. and Newman, R.H., 1990 Structural studies of Silica Springs allophane Clay Minerals 25 329–341.CrossRefGoogle Scholar
Clark, C. and McBride, M.B., 1984 Chemisorption of Cu (II) and Co (II) on allophane and imogolite Clays and Clay Minerals 32 4, 300–311.CrossRefGoogle Scholar
Cradwick, P.D.G. Farmer, V.C. Russell, J.D. Masson, C.R. Wada, K. and Yoshinaga, N., 1972 Imogolite, a hydrated aluminum silicate of tubular structure Nature Physical Science 240 187–189.CrossRefGoogle Scholar
Creton, B. Bougeard, D. Smirnov, K.S. Guilment, J. and Poncelet, O.G., 2008 Structural model and computer modeling study of allophane 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
Farmer, V.C., 1997 Conversion of ferruginous allophanes to ferruginous beidellites at 95° under alkaline conditions with alternating oxidation and reduction Clays and Clay Minerals 45 591–597.CrossRefGoogle Scholar
Farmer, V.C. Fraser, A.R. and Tait, J.M., 1977 Synthesis of imogolite: a tubular aluminium silicate polymer Journal of the Chemical Society, Chemical Communications 13 462–463.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. Krishnamurti, G. and Huang, P., 1991 Synthetic allophane and layer-silicate formation in SiO2-Al2O3-FeO-Fe2O3-MgO-H2O systems at 23°C and 89°C in a calcareous environment Clays and Clay Minerals 39 561–570.CrossRefGoogle Scholar
Galoisy, L. Calas, G. and Arrio, M.A., 2001 High-resolution XANES spectra of iron in minerals and glasses: structural information from the pre-edge region Chemical Geology 174 307–319.CrossRefGoogle Scholar
Gates, W.P. Slade, P.G. Manceau, A. and Lanson, B., 2002 Site occupancies by iron in nontronites Clays and Clay Minerals 50 223–239.CrossRefGoogle Scholar
Goodman, B. Russell, J. Montez, B. Oldfield, E. and Kirkpatrick, R., 1985 Structural studies of imogolite and allophanes by aluminum-27 and silicon-29 nuclear magnetic resonance spectroscopy Physics and Chemistry of Minerals 12 342–346.CrossRefGoogle Scholar
Gustafsson, J.P., 2001 The surface chemistry of imogolite Clays and Clay Minerals 49 73–80.CrossRefGoogle Scholar
Henmi, T. and Wada, K., 1976 Morphology and composition of allophane American Mineralogist 61 379–390.Google Scholar
Hiradate, S. and Wada, S.-I., 2005 Weathering process of volcanic glass to allophane determined by 27Al and 29Si solid-state NMR Clays and Clay Minerals 53 401–408.CrossRefGoogle Scholar
Horikawa, Y. and Soezima, H., 1977 State analysis of iron in allophanic clays II: Iron L-emission band spectra from allophanic clays and hisingerite by the use of an X-ray microanalyzer Clay Science 5 97–102.Google Scholar
Ildefonse, P. Kirkpatrick, R.J. Montez, B. Calas, G. Flank, A.M. and Lagarde, P., 1994 27Al MAS NMR and aluminum X-ray absorption near edge structure study of imogolite and allophanes Clays and Clay Minerals 42 276–287.CrossRefGoogle Scholar
Iyoda, F. Hayashi, S. Arakawa, S. John, B. Okamoto, M. Hayashi, H. and Yuan, G., 2012 Synthesis and adsorption characteristics of hollow spherical allophane nano-particles Applied Clay Science 56 77–83.CrossRefGoogle Scholar
Joussein, E. Petit, S. Churchman, J. Theng, B. Righi, D. and Delvaux, B., 2005 Halloysite clay minerals - a review Clay Minerals 40 383–426.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
Kawano, M. and Tomita, K., 2001 Microbial biomineralization in weathered volcanic ash deposit and formation of biogenic minerals by experimental incubation American Mineralogist 86 400–410.CrossRefGoogle Scholar
Kitagawa, Y., 1973 Substitution of aluminum by iron in allophane Clay Science 4 151–154.Google Scholar
Levard, C. Rose, J. Thill, A. Masion, A. Doelsch, E. Maillet, P. Spalla, O. Olivi, L. Cognigni, A. Ziarelli, F. and Bottero, J.Y., 2010 Formation and growth mechanisms of imogolite-like aluminogermanate nanotubes Chemistry of Materials 22 2466–2473.CrossRefGoogle Scholar
Levard, C. Masion, A. Rose, J. Doelsch, E. Borschneck, D. Olivi, L. Chaurand, P. Dominici, C. Ziarelli, F. Thill, A. Maillet, P. and Bottero, J.Y., 2011 Synthesis of Geimogolite: influence of the hydrolysis ratio on the structure of the nanotubes Physical Chemistry Chemical Physics 13 14516–14522.CrossRefGoogle ScholarPubMed
Levard, C. Doelsch, E. Basile-Doelsch, I. Abidin, Z. Miche, H. Masion, A. Rose, J. Borschneck, D. and Bottero, J.Y., 2012 Structure and distribution of allophanes, imogolite and proto-imogolite in volcanic soils Geoderma 183–184 100–108.CrossRefGoogle Scholar
Li, L. Xia, Y. Zhao, M. Song, C. Li, J. and Liu, X., 2008 The electronic structure of a single-walled aluminosilicate nanotube Nanotechnology 19 175702.CrossRefGoogle ScholarPubMed
MacKenzie, K.J.D. and Cardile, C.M., 1988 The structure and thermal reactions of natural iron-containing allophanes studied by 57-Fe Mössbauer spectroscopy Thermochimica Acta 130 259–267.CrossRefGoogle Scholar
MacKenzie, K. Bowden, M. and Meinhold, R., 1991 The structure and thermal transformations of allophanes studied by 29Si and 27Al high resolution solid-state NMR Clays and Clay Minerals 39 337–346.CrossRefGoogle Scholar
Manceau, A. Bonnin, D. Kaiser, P. and Frétigny, C., 1988 Polarized EXAFS of biotite and chlorite Physics and Chemistry of Minerals 16 180–185.CrossRefGoogle Scholar
Manceau, A. Bonnin, D. Stone, W.E.E. and Sanz, J., 1990 Distribution of Fe in the octahedral sheet of trioctahedral micas by polarized EXAFS; comparison with NMR results Physics and Chemistry of Minerals 17 363–370.CrossRefGoogle Scholar
Manceau, A. Chateigner, D. and Gates, W.P., 1998 Polarized EXAFS, distance-valence least-squares modeling (DVLS), and quantitative texture analysis approaches to the structural refinement of Garfield nontronite Physics and Chemistry of Minerals 25 347–365.CrossRefGoogle Scholar
Manceau, A. Lanson, B. Drits, V.A. Chateigner, D. Gates, W.P. Wu, J. Huo, D. and Stucki, J.W., 2000 Oxidationreduction mechanism of iron in dioctahedral smectites: I. Crystal chemistry of oxidized reference nontronites American Mineralogist 85 133–152.CrossRefGoogle Scholar
McBride, M.B. Farmer, V.C. Russell, J.D. Tait, J.M. and Goodman, B.A., 1984 Iron substitution in aluminosilicate sols synthesized at low pH Clay Minerals 19 1–8.CrossRefGoogle Scholar
Ming, D. W. Mittlefehldt, D. W. Morris, R. V. Golden, D. C. Gellert, R. Yen, A. Clark, B. C. Squyres, S. W. Farrand, W. H. Ruff, S. W. Arvidson, R. E. Klingelhöfer, G. McSween, H. Y. Rodionov, D. S. Schröder, C. de Souza, P. A. and Wang, A., 2006 Geochemical and mineralogical indicators for aqueous processes in the Columbia Hills of Gusev crater, Mars Journal of Geophysical Research: Planets 111 E2 n/a-n/a.CrossRefGoogle Scholar
Miyauchi, N. and Aomine, S., 1966 Mineralogy of gel-like substance in the pumice bed in Kanuma and Kitakami Districts Soil Science and Plant Nutrition 12 19–22.CrossRefGoogle Scholar
Montarges-Pelletier, E. Bogenez, S. Pelletier, M. Razafitianamaharavo, A. Ghanbaja, J. Lartiges, B. and Michot, L., 2005 Synthetic allophane-like particles: textural properties Colloids and Surfaces A: Physicochemical and Engineering Aspects 255 1–10.CrossRefGoogle Scholar
Newville, M., 2001 IFEFFIT: interactive XAFS analysis and FEFF fitting Journal of Synchrotron Radiation 8 322–324.CrossRefGoogle ScholarPubMed
O’Day, P.A. Rehr, J.J. Zabinsky, S.I. Brown, G.E. Jr., 1994 Extended X-ray absorption fine structure (EXAFS) analysis of disorder and multiple-scattering in complex crystalline solids Journal of the American Chemical Society 116 2938–2949.CrossRefGoogle Scholar
Ohashi, F. Wada, S.-I. Suzuki, M. Maeda, M. and Tomura, S., 2002 Synthetic allophane from high-concentration solutions: nanoengineering of the porous solid Clay Minerals 37 451–456.CrossRefGoogle Scholar
Ookawa, M. Inoue, Y. Watanabe, M. Suzuki, M. and Yamaguchi, T., 2006 Synthesis and characterization of Fe containing imogolite Clay Science 12 Suppl.2 280–284.Google Scholar
Ossaka, J. Iwai, S.-i. Kasai, M. Shirai, T. and Hamada, S., 1971 Coexistence states of iron in synthesized iron-bearing allophane (Al2O3-SiO2-Fe2-H2O system) Bulletin of the Chemical Society of Japan 44 716–718.CrossRefGoogle Scholar
Ostergren, J.D. Brown, G.E. Parks, G.A. and Tingle, T.N., 1999 Quantitative speciation of lead in selected mine tailings from Leadville, CO Environmental Science & Technology 33 1627–1636.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
Pokrovski, G.S. Schott, J. Farges, F. and Hazemann, J.-L., 2003 Iron (III)-silica interactions in aqueous solution: insights from X-ray absorption fine structure spectroscopy Geochimica et Cosmochimica Acta 67 3559–3573.CrossRefGoogle Scholar
Rampe, E. Kraft, M. Sharp, T. Golden, D. Ming, D. and Christensen, P., 2012 Allophane detection on Mars with Thermal Emission Spectrometer data and implications for regional-scale chemical weathering processes Geology G33215.33211.CrossRefGoogle Scholar
Ravel, B., 2001 ATOMS: crystallography for the X-ray absorption spectroscopist Journal of Synchrotron Radiation 8 314–316.CrossRefGoogle ScholarPubMed
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
Roberts, D.R. Scheinost, A.C. and Sparks, D.L., 2002 Zinc speciation in a smelter-contaminated soil profile using bulk and microspectroscopic techniques Environmental Science & Technology 36 1742–1750.CrossRefGoogle Scholar
Schwertmann, U. Friedl, J. and Kyek, A., 2004 Formation and properties of a continuous crystallinity series of synthetic ferrihydrites (2- to 6-line) and their relation to FeOOH forms Clays and Clay Minerals 52 221–226.CrossRefGoogle Scholar
Shimizu, H. Watanabe, T. Henmi, T. Masuda, A. and Saito, H., 1988 Studies on allophane and imogolite by high-resolution solid-state 29Si-and 27Al-NMR and ESR Geochemical Journal 22 23–31.CrossRefGoogle Scholar
Tazaki, K. Morikawa, T. Watanabe, H. Asada, R. and Okuno, M., 2006 Microbial formation of imogolite Clay Science 12 Supplement2 245–254.Google Scholar
Toner, B.M. Santelli, C.M. Marcus, M.A. Wirth, R. Chan, C.S. McCollom, T. Bach, W. and Edwards, K.J., 2009 Biogenic iron oxyhydroxide formation at mid-ocean ridge hydrothermal vents: Juan de Fuca Ridge Geochimica et Cosmochimica Acta 73 388–403.CrossRefGoogle Scholar
Tsipursky, S.I. and Drits, V.A., 1984 The distribution of octahedral cations in the 2:1 layers of dioctahedral smectites studied by oblique-texture electron diffraction Clay Minerals 19 177–193.CrossRefGoogle Scholar
Vantelon, D. Montarges-Pelletier, E. Michot, L.J. Pelletier, M. Thomas, F. and Briois, V., 2003 Iron distribution in the octahedral sheet of dioctahedral smectites. An Fe K-edge X-ray absorption spectroscopy study Physics and Chemistry of Minerals 30 44–53.CrossRefGoogle Scholar
Waychunas, G.A. Apted, M.J. and Brown, G.E., 1983 X-ray K-edge absorption spectra of Fe minerals and model compounds: Near-edge structure Physics and Chemistry of Minerals 10 1–9.CrossRefGoogle Scholar
Webb, S.M., 2005 Sixpack: A graphical user interface for XAS analysis using IFEFFIT Physica Scripta T115 1011–1014.CrossRefGoogle Scholar
Westre, T.E. Kennepohl, P. DeWitt, J.G. Hedman, B. Hodgson, K.O. and Solomon, E.I., 1997 A multiplet analysis of Fe K-edge 1s → 3d pre-edge features of iron complexes Journal of the American Chemical Society 119 6297–6314.CrossRefGoogle Scholar
Yucelen, G.I. Choudhury, R.P. Vyalikh, A. Scheler, U. Beckham, H.W. and Nair, S., 2011 Formation of single-walled aluminosilicate nanotubes from molecular precursors and curved nanoscale intermediates Journal of the American Chemical Society 133 5397–5412.CrossRefGoogle ScholarPubMed