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Weathering Process of Volcanic Glass to Allophane Determined by 27Al and 29Si Solid-State NMR

Published online by Cambridge University Press:  01 January 2024

Syuntaro Hiradate  and
Shin-Ichiro Wada
Syuntaro Hiradate*
Affiliation:
Department of Biological Safety Science, National Institute for Agro-Environmental Sciences (NIAES), 3-1-3 Kan-nondai, Tsukuba, Ibaraki 305-8604, Japan
Shin-Ichiro Wada
Affiliation:
Faculty of Agriculture, Kyushu University, Fukuoka 812-8581, Japan
*
*E-mail address of corresponding author: [email protected]
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Abstract

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To clarify the weathering process of volcanic glass to allophane, solid-state 29Si and 27Al magic angle spinning (MAS) nuclear magnetic resonance (NMR) signals of four Japanese volcanic glasses and two (Al- and Si-rich) allophanes were assigned. The volcanic glasses showed a broad 29Si NMR signal between −80 and −120 ppm with the peak centered at ~ −104 ppm, indicating that they were rich in Si-O-Si bridging structure (silica gel-like polymer Si). Aluminum was present in tetrahedral form in the four volcanic glass samples. In both Al- and Si-rich allophanes, octahedral Al (3 ppm by 27Al NMR) and imogolite-like Si (Q33VIAl, −78 ppm by 29Si NMR) were the major components. In a Si-rich allophane, NMR signals centered at around −85 ppm for 29Si and 55 ppm for 27Al were also observed, although it is possible that those signals were derived from impurities. Impurities could have originated from the soils and/or been unexpectedly synthesized during the purification procedures, e.g. during hot 2% Na2CO3 treatments. Based on the NMR spectra of size-fractionated soil samples, the weathering process of volcanic glass to allophane was proposed as follows: (1) dissolution of Al from volcanic glass accompanied by the transformation of IVAl to VIAl; (2) formation of a gibbsite-like sheet resulting from the hydrolysis of the dissolved Al; (3) dissolution of silica gel-like polymer Si in volcanic glass resulting in the formation of monosilicic acid; and (4) formation of Si(OH)(OVI,Al)3 structure (Q33VIAl) as a result of the reaction between the gibbsite-like sheet and the monosilicic acid. These formation reactions of allophane could occur in solution as well as on the surface of volcanic glass.

Keywords

AllophaneImogoliteSolid-state MAS NMRSpeciation of 27Al and 29SiVolcanic Glass
Type
Research Article
Information
Clays and Clay Minerals , Volume 53 , Issue 4 , August 2005 , pp. 401 - 408
Copyright
Copyright © The Clay Minerals Society 2005

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