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Weathering process of volcanic glass to allophane determined by 27Al and 29Si solid-state NMR

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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 (Q3 3VIAl, −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)(OVIAl)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.
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Keywords: ALLOPHANE; IMOGOLITE; SOLID-STATE MAS NMR; SPECIATION OF 27AL AND 29SI; VOLCANIC GLASS

Document Type: Research Article

Publication date: August 1, 2005

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  • The JOURNAL publishes articles of interest to the international community of clay scientists, including but not limited to areas in mineralogy, crystallography, geology, geochemistry, sedimentology, soil science, agronomy, physical chemistry, colloid chemistry, ceramics, petroleum engineering, foundry engineering, and soil mechanics. Clays and Clay Minerals exists to disseminate to its worldwide readership the most recent developments in all of these aspects of clay materials. Manuscripts are welcome from all countries.

    Clays and Clay Minerals is the official publication of The Clay Minerals Society.

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