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On the mechanisms of apophyllite alteration in aqueous solutions. A combined AFM, XPS and MAS NMR study

Published online by Cambridge University Press:  01 January 2024

Kirill Aldushin ,
Guntram Jordan ,
Michael Fechtelkord ,
Wolfgang W. Schmahl ,
Hans-Werner Becker  and
Werner Rammensee
Kirill Aldushin
Affiliation:
Institut für Geologie, Mineralogie und Geophysik, Ruhr-Universität Bochum, 44780 Bochum, Germany Institut für Mineralogie und Geochemie, Universität zu Köln, Zülpicher Str. 49b, 50674 Köln, Germany
Guntram Jordan*
Affiliation:
Institut für Geologie, Mineralogie und Geophysik, Ruhr-Universität Bochum, 44780 Bochum, Germany
Michael Fechtelkord
Affiliation:
Institut für Geologie, Mineralogie und Geophysik, Ruhr-Universität Bochum, 44780 Bochum, Germany
Wolfgang W. Schmahl
Affiliation:
Institut für Geologie, Mineralogie und Geophysik, Ruhr-Universität Bochum, 44780 Bochum, Germany
Hans-Werner Becker
Affiliation:
Institut fur Physik mit Ionenstrahlung (Exp. Physik III), Ruhr-Universität Bochum, 44780 Bochum, Germany
Werner Rammensee
Affiliation:
Institut für Mineralogie und Geochemie, Universität zu Köln, Zülpicher Str. 49b, 50674 Köln, Germany
*
*E-mail address of corresponding author: guntram.jordan@ruhr-uni-bochum.de
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Abstract

Apophyllite, a hydrous K-Ca-phyllosilicate, reacts with acidic aqueous solutions at room temperature. Various analytical methods have been applied to study the mechanism of the reaction and its characteristics, i.e. the changes in chemical composition, modifications in crystal structure and alterations in surface morphology. In contact with acidic solution, protonation of the terminal, non-bridging oxygen at the silicate tetrahedra takes place and the interlayer cations K+ and Ca2+ are removed. The protonation and ion removal causes the interlayer spacing to increase. Atomic force microscopy shows that the increase takes place discontinuously and, therefore, reflects a discontinuous reaction that comprises a two- or three-step protonation. Additionally, three structurally different protonation sites have been detected by nuclear magnetic resonance spectroscopy which also differ in the amount of close-by hydrogen, although in pristine apophyllite all terminal oxygen positions at silicate tetrahedra are structurally equivalent. In many clay minerals such structurally different protonation sites have not been detected so far. Thus, the multi-step protonation process in apophyllite clearly demonstrates the vast sensitivity of the protonation reaction on small structural variations in phyllosilicates.

Keywords

Acidic LeachingApophylliteAtomic Force MicroscopyCation ExchangeCrystalline Silicic AcidDissolutionNuclear Magnetic Resonance SpectroscopyPhyllosilicatesSurface AlterationSwelling
Type
Research Article
Information
Clays and Clay Minerals , Volume 52 , Issue 4 , August 2004 , pp. 432 - 442
Copyright
Copyright © The Clay Minerals Society 2004

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