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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

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