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Structural studies of Silica Springs allophane

Published online by Cambridge University Press:  09 July 2018

C.W. Childs ,
R.L. Parfitt  and
R.H. Newman
C.W. Childs
Affiliation:
Division of Land and Soil Sciences, New Zealand
R.L. Parfitt
Affiliation:
Division of Land and Soil Sciences, New Zealand
R.H. Newman
Affiliation:
Chemistry Division, DSIR, Lower Hutt, New Zealand
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Abstract

The structure of Silica Springs allophane from New Zealand has been studied by high-resolution 27A1 and 29Si NMR spectroscopy, IR spectroscopy and electron microscopy. Experimental NMR conditions were chosen to give a quantitative relationship between signal strength and Al content. Aluminium is present in both octahedral (Alvi) and tetrahedral (Aliv) coordination, and the ratio Alvi:Aliv was obtained for three samples with different total Al:Si ratios. In all cases the Aliv:Si ratio was 1 : 3, consistent with the ratio in ideal muscovite. The negative charge arising from Aliv was apparently balanced by positive charge at adjacent Alvi sites. Both NMR and IR spectra indicate that Si exists in a condensed network, probably a sheet, with Si atoms linked (through oxygen) to one, two and, possibly, three other Si atoms, but not four. The spectra are consistent with a mixture of Si-O-Si, Si-O-Al, and Si-OH linkages. A structure based on fragments of single curved 1 : 1 aluminosilicate layers, with the tetrahedral sheet on the outer surfaces, is suggested, the diameter of curvature being 2–3 nm. The tetrahedral sheet is more or less complete and has a Aliv : Si ratio of 1 : 3; the octahedral Alvi sheet is incomplete. Electron micrographs suggest that, at least in some cases, the fragments form more or less complete spherules. This proposal seems to accord with Farmer's concept of “aluminous hydrous feldspathoids”. The minimum pH at which Silica Springs allophane has precipitated corresponds to the initial presence of tetrahedrally coordinated Al species in solution.

Type
Research Article
Information
Clay Minerals , Volume 25 , Issue 3 , September 1990 , pp. 329 - 341
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1990

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References

References

Drever, J.I. (1982) The Geochemistry of Natural Waters, pp. 68–59. Prentice-Hall, Englewood Cliffs, New Jersey.Google Scholar
Fanning, D.S. Keramidas, V.Z. (1977) Micas. Pp. 195–258 in: Minerals in Soil Environments (J.B, Dixon S.B. Weed, editors). Soil Sci. Soc. Am,, Madison.Google Scholar
Farmer, V.C. (1987) Synthetic and natural allophane and imogolite: a synergistic relationship. Trans. XIII Congr. Int. Soc. Soil Sci. 5, 346–354.Google Scholar
Farmer, V.C. Russell, J.D. (1990) The structure and genesis of allophanes and imogolite; their distribution in non-volcanic soils. In: Soil Colloids and the Association in Soil Aggregates. Proc. NATO Advanced Studies Workshop, Ghent, 1985. Plenum, New York.Google Scholar
Farmer, V.C., Fraser, A.R. & Tait, J.M. (1979) Characterization of the chemical structures of natural and synthetic aluminosilicate gels and sols by infrared spectroscopy. Geochim. Cosmochim. Acta 23, 1417–1420.Google Scholar
Goodman, B.A., Russell, J.D., Montez, B., Oldfield, E. & Kirkpatrick, R.J. (1985) Structural studies of imogolite and allophanes by aluminium-27 and silicon-29 nuclear magnetic resonance spectroscopy. Phys. Chem. Miner. 12, 342–346.Google Scholar
Lippmaa, E., Magi, M., Samoson, A., Engelhardt, G. & Grimmer, A.-R. (1980) Structural studies of silicates by solid- state high-resolution 29Si NMR. J. Am. Chem. Soc. 102, 4889–4893.Google Scholar
Lippmaa, E & Magi, M.， Samoson, A., Tarmak, M. & Engelhardt, G. (1981) Investigation of the structure of zeolites by solid-state high-resolution 29Si NMR spectroscopy. J. Am. Chem. Soc. 103, 4992–4996.CrossRefGoogle Scholar
Maciel, G.E. & Sindorf, D.W. (1980) Silicon-29 nuclear magnetic resonance study of the surface of silica gel by cross polarization and magic-angle spinning. J. Am. Chem. Soc. 102, 7606–7607.CrossRefGoogle Scholar
Merino, E., Harvey, C., & Murray, H.H. (1989) Aqueous-chemical control of the tetrahedral-aluminum content of quartz，halioysite, and other low-temperature silicates. 37, 135–142.Google Scholar
Moenke, H.M.W. (1974) Silica, the three-dimensional silicates, borosilicates and beryllium silicates. Pp. 365–382 in: The Infrared Spectra of Minerals (V.C. Farmer, editor). Mineralogical Society, London.CrossRefGoogle Scholar
Parfitt, R.L. (1990) Allophane in New Zealand—a review. Aust. J. Soil Res. 28, 343–360.CrossRefGoogle Scholar
Parfitt, R.L. & Henmi, T. (1980) Structure of some allophanes from New Zealand. Clays Clay Miner. 28, 285–294.Google Scholar
Parfitt, R.L. & Kimble, J.M. (1989) Conditions for formation of allophane in soils. Soils. Sci. Soc. Am. J. 53, 971–977.Google Scholar
Parfitt, R.L., Furkert, R.J. & Henmi, T. (1980) Identification and structure of two types of allophane from volcanic ash soils*and tephra. Clays Clay Miner. 28, 328–334.Google Scholar
Sanz, J. & Serratosa, J.M. (1984) 29Si and 27Al high-resolution MAS-NMR spectra of phyllosilicates. J. Am. Chem. Soc. 106, 4790–4793.CrossRefGoogle Scholar
Theng, B.K.G., Russell, M., Churchman, G.J. & Parfitt, R.L. (1982) Surface properties of allophane, imogolite and halloysite. Clays Clay Miner. 30, 143–149.CrossRefGoogle Scholar
Wada, K. (1979) Structural formulas of allophane. Proc. Int, Clay Conf. Oxford, 537-545.Google Scholar
Wada, K. & Yoshinaga, N. (1969) The structure of imogolite. Am. Miner. 54, 50–71.Google Scholar
Wells, N., Childs, C.W. & Downes, C.J. (1977) Silica Springs, Tongariro National Park, New Zealand—analyses of the spring water and characterisation of the alumino-silicate deposit. Geochim. Cosmochim. Acta 41, 1497–1506.CrossRefGoogle Scholar
Wilson, M.A., Wada, K., Wada, S.I. & Kakuto, Y. (1988) Thermal transformations of synthetic allophane and imogolite as revealed by nuclear magnetic resonance. Clay Miner. 23, 175–190 CrossRefGoogle Scholar

Appendix References

Fenzke, D., Freude, D., Fröhlich, T. Haase, J. (1984) NMR intensity measurements of half-integer quadrupole nuclei. Chem. Phys. Lett. 111, 171–175.CrossRefGoogle Scholar
Hoult, D.I., Chen, C.-N., Eden, H. Eden, M. (1983) Elimination of baseline artifacts in spectra and their integrals. J. Magn. Reson. 51, 110–117.Google Scholar
Lampe, F.V., Muller, D., Gessner, W., Grimmer, A.-R. Scheler, G. (1982) Vergleichende 27A1-NMR- Untersuchungen am Mineral Zunyit und basischen Aluminium-Salzen mit tridekameren Al-oxo-hydroxo-aquo-Kationen. Z. anorg. allg. Chem. 489, 16–22.CrossRefGoogle Scholar
Muller, D., Berger, G., Grunze, I., Ladwig, G., Hallas, E. Haubenreisser, U. (1983) Solid-state high-resolution 27A1 nuclear magnetic resonance studies of the structure of CaO-Al2O3-P2O5 glasses. Phys. Chem. Glasses 24, 37–42.Google Scholar
Sanz, J. Serratosa, J.M. (1984) 29Si and 27AI high-resolution MAS-NMR spectra of phyllosilicates. J. Am. Soc. 106, 4790–4793.Google Scholar