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Iron in soil kaolins from Indonesia and Western Australia

Published online by Cambridge University Press:  09 July 2018

R. D. Hart ,
T. G. St Pierre ,
R. J . Gilkes ,
A. J. McKinley ,
S. Siradz  and
Balwant Singh
R. D. Hart*
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Perth, W.A. 6009
T. G. St Pierre
Affiliation:
Department of Physics, University of Western Australia, Perth, W.A. 6009
R. J . Gilkes
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Perth, W.A. 6009
A. J. McKinley
Affiliation:
Department of Chemistry, University of Western Australia, Perth, W.A. 6009, Australia
S. Siradz
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Perth, W.A. 6009
Balwant Singh*
Affiliation:
Department of Soil Science and Plant Nutrition, University of Western Australia, Perth, W.A. 6009
*
*E-mail: r.d.hart@exchange.curtin.edu.au
†Present address: Department of Agricultural Chemistry and Soil Science, University of Sydney, Australia
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Abstract

Soil kaolins from Indonesia and Western Australia and a range of reference kaolins were studied using Mössbauer spectroscopy, electron paramagnetic resonance (EPR) spectroscopy and SQUID magnetometry. Mössbauer spectra indicate that the Fe within the kaolins is in the highspin Fe3+ oxidation state and that a large fraction of the Fe is present as dispersed atoms residing within the octahedral sites of the kaolinite crystal structure. The EPR spectra are typical for soil kaolins except for the absence of radiation-induced defects for the Indonesian kaolins. The Fe(I) spectra are dominant with a strong symmetric peak at g= 4.3, the presence of Fe(II) spectra is shown by a shoulder on this peak at g= 4.9 and a small phase up peak at g= 9.2.

Low-temperature (5 K) magnetization (M) measurements over large field (H) sweeps (±70 kOe) yielded M(H) curves which are fitted well with Brillouin functions indicating the paramagnetic nature of the kaolins at temperatures down to 5 K. A very small remanent magnetization was detectable in the kaolins. Remanent magnetization to saturation magnetization ratios ranged from 10–4 to 10–3 for the Indonesian kaolins and were all ∼10–3 for the Western Australian kaolins, indicating that at high fields the vast majority of the magnetization of the kaolins is due to paramagnetic ions.

Zero-field-cooled and field-cooled magnetization measurements in small fields (500 Oe) indicate that the Indonesian kaolins are generally free from magnetically-blocked material down to a temperature of 5 K. The magnetic susceptibility of the Indonesian kaolins shows Curie Law behaviour indicating paramagnetic behaviour over all temperatures down to 5 K. Measurements on the Western Australian kaolins indicated the presence of some magnetic material that is magnetically blocked at temperatures below ∼200 ­ 250 K. As a consequence, the magnetic susceptibility showed large deviations from Curie Law behaviour.

Keywords

ironsoilkaolinIndonesiaAustraliaMössbauer spectroscopyelectron paramagnetic resonanceSQUID magnetometry
Type
Research Article
Information
Clay Minerals , Volume 37 , Issue 4 , December 2002 , pp. 671 - 685
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2002

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References

Angel, B.E. and Vincent, W.E.J. (1978) Electron spin resonance studies of iron oxides associated with the surface of kaolins. Clays and Clay Minerals, 26, 263–272.Google Scholar
A.P.I., (1951) Reference Clay Minerals. American Petroleum Institute, Project 49, Preliminary Reports, New York.Google Scholar
Bahranowski, J., Serwicka, E.M., Stoch, L. & Strycharski, P. (1993) On the possibility of removal of nonstructural iron kaolinite-g roup minerals. Clay Minerals, 28, 379–391.Google Scholar
Berger, R., Kliava, J., El-Mostapha, Y., Bissey, J.-C., Zinsou, P.K. and Beziade, P. (1995) Diluted and nondiluted ferric ions in borate glasses studied by electron paramagnetic resonance. Journal of Non- Crystalline Solids, 180, 151–163.CrossRefGoogle Scholar
Berger, R., Bissey, J.-C., Kliava, J. & Soulard, B. (1997) Superparamagnetic resonance of ferric ions in devitrified borate glass. Journal of Magnetism and Magnetic Materials, 167, 129–135.CrossRefGoogle Scholar
Balan, E.T., Allard, T., Boizot, B., Morin, G. & Muller, J.- P. (1999) Structural Fe3+ in natural kaolinites: new insights from electron paramagnetic resonance spectra fitting at X and Q-band frequencies. Clays and Clay Minerals, 47, 605–616.Google Scholar
Bonnin, D., Muller, S. & Calas, G. (1982) Le fer dans les kaolins. Etude par spectrometries RPE, Mössbauer, EXAFS. Bulletin Minéralogie, 105, 467–475.Google Scholar
Brindley, G.W., Kao, C.-C., Harrison, J.L., Lipsicas, M. & Raythatha, R. (1986) Relation between structural disorder and other characteristics of kaolinites and dickites. Clays and Clay Minerals, 34, 239–249.Google Scholar
Calas, G. (1988) Electron paramagnetic resonance. Pp. 513–563 in. Spectroscopic Methods in Mineralogy and Geology (Hawthorne, F.C., editor). Reviews in Mineralogy, 18. Mineralogical Society of America, Washington, D.C.Google Scholar
Clozel, B.T., Allard, T. & Muller, J.-P. (1994) Nature and stability of radiation induced defects in natural kaolinites: new results and a reappraisal of published works. Clays and Clay Minerals, 42, 657–666.CrossRefGoogle Scholar
Coey, J.M.D. & Ghose, S. (1988) Magnetic phase transition in silicate minerals. Advances in Physical Geochemistry, 17, 162–184.CrossRefGoogle Scholar
Coey, J.M.D., Ballet, O., Moukarika, A. & Soubeyroux, J.L. (1981) Magnetic properties of sheet silicates, 1:1 layer minerals. Physics and Chemistry of Minerals, 7, 141–148.CrossRefGoogle Scholar
Coyne, L.M. & Banin, A. (1986) Effect of adsorbed iron on thermoluminescence and electron spin spectra of Ca-Fe exchanged montmorillonite. Clays and Clay Minerals. 34, 645–650.CrossRefGoogle ScholarPubMed
Delineau, T., Allard, T., Muller, J.-P., Barres, O., Yvon, J. & Cases, J.-M. (1994) FTIR reflectance vs EPR studies of structural iron in kaolinites. Clays and Clay Minerals, 42, 308–320.CrossRefGoogle Scholar
Fysh, S.A., Cashion, J.D. & Clark, P.E. (1983a) Mössbauer effect studies of iron in kaolin I. Structural iron. Clays and Clay Minerals, 31, 285–292.CrossRefGoogle Scholar
Fysh, S.A., Cashion, J.D. & Clark, P.E. (1983b) Mössbauer effect studies of iron in kaolin II. Surface iron. Clays and Clay Minerals, 31, 293–298.Google Scholar
Gaite, J.M., Ermakoff, P. & Muller, J.-P. (1993) Characterisation and origin of two Fe3+ EPR spectra in kaolinite. Physics and Chemistry of Minerals, 20, 242–247.CrossRefGoogle Scholar
Hall, P.L. (1980) The application of electron spin resonance spectroscopy to studies of clay minerals: I. Isomorphous substitutions and external surface properties. Clay Minerals, 15, 321–335.CrossRefGoogle Scholar
Hart, R.D., Gilkes, R.J., Singh, B. & Siradz, S. (2002) Nature of soil kaolins from Indonesia and Western Australia. Clays and Clay Minerals, 50, 198–209.Google Scholar
Herbillon, A.J., Mestdagh, M.M., Vielvoye, L. & Derouane, E.G. (1976) Iron in kaolinite with special reference to kaolinite from tropical soils. Clay Minerals, 11, 201–220.CrossRefGoogle Scholar
Hughes, J.C. & Brown, G. (1979) A crystallinity index for soil kaolins and its relation to parent rock, climate and maturity. Journal of Soil Science, 30, 557–563.CrossRefGoogle Scholar
Jepson, W.B. & Rowse, J.B. (1975) The composition of kaolinite ­ an electron microprobe study. Clays and Clay Minerals, 23, 310–317.CrossRefGoogle Scholar
Jones, J.P.E., Angel, B.E. & Hall, P.L. (1974) Electron spin resonance studies of doped synthetic kaolinite: II. Clay Minerals, 10, 257–270.CrossRefGoogle Scholar
Kittel, C. (1996) An Introduction to Solid State Physics, 7th edition. Wiley, New York.Google Scholar
Kliava, J. & Berger, R. (1999) Size and shape distribution of magnetic nanoparticles in disordered systems: computer simulations of superparamagnetic resonance spectra. Jounal of Magnetism and Magnetic Materials, 205, 328–342.CrossRefGoogle Scholar
Komusinski, J., Stoch, L. & Dubiel, S.M. (1981) Application of electron paramagnetic resonance and Mössbauer spectroscopy in the investigation of kaolin group minerals. Clays and Clay Minerals, 29, 23–30.Google Scholar
Malden, P.J. & Meads, R.E. (1967) Nature, 215, 844–846.CrossRefGoogle Scholar
Malengrau, N., Muller, J.­P. & Calas, G. (1994) Fespeciation in kaolins: a diffuse reflectance study. Clays and Clay Minerals, 42, 137–147.Google Scholar
Meads, R.E. & Malden, P.J. (1975) Electron spin resonance in natural kaolinites containing Fe3+ and other transition metal ions. Clay Minerals, 10, 313–345.CrossRefGoogle Scholar
Mehra, O.P. & 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.Google Scholar
Mestdagh, M.M., Vielvoye, L. & Herbillon, A.J. (1980) Iron in kaolinite: II. The relationship between kaolinite crystallini ty and iron content. Clay Minerals, 15, 1–13.Google Scholar
Morrish, A.H. (1965) The Physical Principles of Magnetism. Wiley, New York.Google Scholar
Muller, J.-P., Ildefonse, Ph. & Calas, G. (1990) Paramagnetic defect centres in hydrothermal kaolinite from an altered tuff in the Nopal uranium deposit, Chihuahua, Mexico. Clays and Clay Minerals, 38, 600–608.Google Scholar
Murad, E. & Wagner, U. (1991) Mössbauer spectra of kaolinite, halloysite and the firing products of kaolinite. New results and a reappraisal of published work. Neues Jahrbuch für Mineralogie Abhandlungen, 162, 281–309.Google Scholar
Newman, A.C.D. (1987) The interaction of water with clay mineral surfaces. In: Chemistry of Clays and Clay Minerals (Newman, A.C.D., editor). Mineralogical Society Monograph 6. Longman Scientific and Technical, Harlow, Essex, UK.Google Scholar
Rancourt, D.G. Christie, I.A.D., Lamarche, G., Swainson, I. & Flandrois, S. (1994) Magnetism of synthetic and natural annite mica: ground state and nature of excitations in an exchange-wise two dimensional easy-plane ferromagnet with disorder. Journal of Magnetism and Magnetic Materials, 138, 31–44.CrossRefGoogle Scholar
Schroeder, P.A. & Pruett, R.J. (1996) Fe ordering in kaolinite: Insights from 29Si and 27Al MAS NMR Spectroscopy. American Mineralogist, 81, 26–38.Google Scholar
Schroeder, P.A., Pruett, R.J. & Hurst, V.J. (1998) Effects of secondary iron phases on kaolinite 27Al MAS NMR Spectra. Clays and Clay Minerals, 46, 429–435.CrossRefGoogle Scholar
Singh, B. (1991) Mineralogical and chemical characteristics of soils from south-western Australia. PhD thesis, University of Western Australia.Google Scholar
Singh, B. & Gilkes, R.J. (1992) Properties of soil kaolins from south-western Australia. Journal of Soil Science, 43, 645–667.CrossRefGoogle Scholar
Singh, B. & Gilkes, R.J. (1995) Application of analytical transmission electron microscopy to identifying intercrystal variations in the composition of clay minerals. Analyst, 120, 1335–1339.CrossRefGoogle Scholar
Siradz, S. (2001) Mineralogical and chemical characteristics of soils from Indonesia. PhD thesis, University of Western Australia.Google Scholar
St Pierre, T.G., Singh, B., Webb, J. & Gilkes, R.J. (1992) Mössbauer spectra of soil kaolins from southwestern Australia. Clays and Clay Minerals, 40, 341–346.CrossRefGoogle Scholar
Stone, W.E. & Torres-Sanchez, R.-M. (1988) Nuclear magnetic resonance spectroscopy applied to minerals. Journal of the Chemical Society: Faraday Transactions, 84, 117–132.Google Scholar
Weaver, C.E. (1976) The nature of TiO2 in kaolinite. Clays and Clay Minerals, 24, 215–218.CrossRefGoogle Scholar