Hostname: page-component-78c5997874-ndw9j Total loading time: 0 Render date: 2024-11-16T15:25:13.205Z Has data issue: false hasContentIssue false

X-ray photoelectron spectroscopic characterization of Silica Springs allophane

Published online by Cambridge University Press:  09 July 2018

C. W. Childs
Affiliation:
School of Chemical and Physical Sciences, Hctoria University, PO Box 600, Wellington 1, New Zealand
K. Inoue
Affiliation:
Faculty of Agriculture, lwate University, 3-18-8 Ueda, Morioka 020, Japan
H. Seyama
Affiliation:
National Institute for Environmental Studies, Tsulatba 305, Japan
M. Soma
Affiliation:
National Institute for Environmental Studies, Tsulatba 305, Japan
B. K. G. Theng
Affiliation:
Manaaki Whenua-Landcare Research, Private Bag 11-052, Palmerston North, New Zealand
G. Yuan
Affiliation:
National Institute for Environmental Studies, Tsulatba 305, Japan

Abstract

A range of allophane samples (atomic AI/Si bulk ratios 1.1-1.9) from Silica Springs, New Zealand, has been characterized by X-ray photoelectron spectroscopy (XPS). Binding energies of Si 2s, Si 2p, Al 2p, O 1s, C 1s, and N 1s electrons, together with the kinetic energies of Al KL23L23 Auger electrons, at or near the surface of allophane aggregates, have been derived. The values for Al, Si and O electrons are similar to those for kaolinite but also to those for some framework silicates (feldspars) having 4-coordinate Al. Values for N electrons suggest that N occurs in organic structures. Comparison of XPS and bulk Al/Si ratios shows an enrichment of Al at or near the surface of allophane aggregates. The same is true for C and N. Extraction with citrate-dithionite-bicarbonate (CDB) reagent leaves the surfaces depleted in Al. The CDB extracts have higher Al/Si ratios than the bulk allophanes. Similarly, CDB treatment reduces the degree of surface enrichment of C and N. Small increases in the binding energies of Si electrons following CDB treatment suggest partial dissolution of the bulk structure though a concomitant removal of a separate phase or species cannot be ruled out. The results may be accounted for in terms of the structure previously suggested for the primary spherules of Silica Springs allophane (Childs et al., 1990) though the composition of the spherules at or near the surface of the allophane aggregates is different from those of the bulk.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 1997

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

Childs, C.W., Parfitt, R.L. & Newman, R.H. (1990) Structural studies of Silica Springs allophane. Clay Miner. 25, 329341.Google Scholar
Defosse, C. & Rouxhet, P.G. (1980) Introduction to X-ray photoelectron spectroscopy. Pp. 169–203 in: Advanced Chemical Methods for Soil and Clay Mineral Research (Stucki, J.W. & Banwart, W.L., editors). D. Reidel, Dordrecht.Google Scholar
Farmer, V.C., Fraser, A.R. & Tait, J.M. (1979) Characterisation of the chemical structures of natural and synthetic aluminosilicate gels and sols by infrared spectroscopy. Geochim. Cosmochim. Acta. 43, 14171420.Google Scholar
He, H., Barr, T.L. & Klinowski, J. (1995) ESCA and solid-state NMR studies of allophane. Clay Miner. 30, 201209.Google Scholar
Inoue, K. & Yoshida, M. (1990) Composition and behaviour of aluminium ions and colloidal aluminosilicates in acidified terrestrial waters. Soil Sci. Plant Nutr. 36, 461468.Google Scholar
Inoue, K., Yoshida, M. & Henmi, T. (1980) The occurrence of allophane in stream deposits from Shishigahana at the northern foot of Mt. Chokai, Japan. Clay Sci. 5, 267276.Google Scholar
Paterson, E. & Swaffield, R. (1994) X-ray photoelectron spectroscopy. Pp. 226–259 in: Clay Mineralogy: Spectroscopic and Chemical Determinative Methods (Wilson, M.J., editor). Chapman & Hall, London.Google Scholar
Seyama, H. & Soma, M. (1985) Bonding-state characterization of the constituent elements of silicate minerals by X-ray photoelectron spectroscopy. J.. Chem. Soc. Faraday Trans. 1, 81, 485495.Google Scholar
Seyama, H. & Soma, M. (1988) Application of X-ray photoelectron spectroscopy to the study of silicate minerals. Research Report 111. National Institute for Environmental Studies, Tsukuba. 121p.Google Scholar
Shoji, S., Nanzyo, M. & Dahlgren, R. (1993) Volcanic Ash Soils, pp. 113 – 116. Developments in Soil Science 21, Elsevier, Amsterdam.Google Scholar
Soma, M., Churchman, G.J. & Theng, B.K.G. (1992) Xray photoelectron spectroscopic analysis of halloysites with different composition and particle morphology. Clay Miner. 27, 413421.Google Scholar
Soma, M., Seyama, H., Yoshinaga, N., Theng, B.K.G. & Childs, C.W. (1996) Bonding state of silicon in natural ferrihydrites by X-ray photoelectron spectroscopy. Clay Sci. 9, 385391.Google Scholar
Theng, B.K.G., Russell, M., Churchman, G.J. & Parfitt, R.L. (1982) Surface properties of allophane, halloysite, and imogolite. Clays Clay Miner. 30, 143149.Google Scholar
Wada, K. (1980) Mineralogical characteristics of Andisols. Pp. 87-107 in: Soils with Variable Charge (Theng, B.K.G., editor). N.Z. Soc. Soil Sci., Lower Hutt.Google Scholar
Wada, K. (1989) Allophane and imogolite. Pp. 1051 – 1087 in: Minerals in Soil Environments (Dixon, J.B. & Weed, S.B., editors). Soil Sci. Soc. Am., Madison.Google Scholar
Wada, K. (1995) Structure and formation of non- and para-crystalline aluminosilicate clay minerals: a review. Proc. 10th Int. Clay Conf., Adelaide, 443-448.Google Scholar
Wada, K. & Greenland, D.J. (1970) Selective dissolution and differential infrared spectroscopy for characterization of ‘amorphous’ constituents soil clays. Clay Miner 8, 241254.CrossRefGoogle Scholar
Wada, K. & Tokashiki, Y. (1972) Selective dissolution and difference infrared spectroscopy in quantitative mineralogical analysis of volcanic-ash soil clays. Geoderma, 7, 199213.Google Scholar
Wada, S-I. & Wada, K. (1980) Formation, composition and structure of hydroxy-aluminosilicate ions. J. Soil Sci. 31, 457467.CrossRefGoogle Scholar
Wells, N. & Theng, B.K.G. (1985) Factors affecting the flow behaviour of soil allophane suspensions under low shear rate. J. Coll, lnterF Sci. 104, 398408.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. cta, 41, 14971506.Google Scholar
Whitton, J.S. & Churchman, G.J. (1987) Standard methods for mineral analysis of soil survey samples for characterisation and classification in NZ Soil Bureau. NZ Soil Bureau Sci. Report, 79, 27p.Google Scholar
Yoshinaga, N. (1986) Mineralogical characteristics: clay minerals. Pp. 41–56 in: Ando Soils in Japan (Wada, K., editor). Kyushu University Press, Fukuoka.Google Scholar