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How can Li be incorporated into the structure of Al-rich tourmaline?

Published online by Cambridge University Press:  27 June 2025

Peter Bačík Open the ORCID record for Peter Bačík [Opens in a new window]  and
Andreas Ertl
Peter Bačík*
Affiliation:
Department of Mineralogy, Petrology and Economic Geology, Faculty of Natural Sciences, Comenius University in Bratislava, Bratislava, Slovak Republic Earth Science Institute, Slovak Academy of Sciences, Bratislava, Slovakia
Andreas Ertl
Affiliation:
Mineralogisch-Petrographische Abt., Naturhistorisches Museum, Wien, Austria Institut für Mineralogie und Kristallographie, Universität Wien, Wien, Austria
*
Corresponding author: Peter Bačík; Email: peter.bacik@uniba.sk
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Abstract

Aluminium-rich tourmaline can contain significant amounts of Li. Until now, syntheses have not been successful in producing Li-rich tourmalines. Because it is still not clear how Li enters the Y site in tourmaline, possible short-range orders, including Li, are discussed using bond valence calculations. Structural arrangement graphs of the Y-site neighbourhood in the structure of elbaitic tourmalines were investigated to determine more information about their stability. Possible short-range ordering including Al and Li at the Y sites, with Na, Ca or □ (vacancy) at the X site, with Si (and Al or B) at the T sites and either (OH) or F at the W site were investigated. Tourmaline with varying amounts of Na but no Ca can only contain ≤1 apfu (atoms per formula unit) YLi. This is consistent with the composition of synthetic tourmaline. Tourmaline with higher Li content (Li >1 apfu) can form when Ca is included. Such tourmaline requires fluorine because more Li results in O1 underbonding, whereas more Al at the Y site leads to O1 overbonding. Underbonding of O1 is preferable for F because OH at the O1 site usually has a bond valence sum (BVS) higher than 1.00 vu (valence units) due to hydrogen bonding of H to ring oxygen atoms. Therefore, liddicoatitic tourmaline is enriched in F and is usually F-dominant. If no fluorine is available in the starting material of a tourmaline synthesis, it is likely that significant proportions of cations such as B and Al will be incorporated into the tetrahedral site. Ultimately, however, only a smaller proportion of Li can be incorporated. Tourmalines with such tetrahedral cations, which also contain a significant Ca content, could theoretically also have significant Y-site vacancies. In order to synthesise Li-rich tourmalines, we would therefore recommend that the starting material also contains both Ca and F.

Keywords

lithium-rich tourmalinealuminium-rich tourmalinecrystal structurebond valence calculationsshort-range orderstourmaline synthesis

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Type
Article
Information
Mineralogical Magazine , First View , pp. 1 - 13
Copyright
© The Author(s), 2025. Published by Cambridge University Press on behalf of The Mineralogical Society of the United Kingdom and Ireland.

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Footnotes

This paper is part of a collection in tribute to the work of Edward Grew at 80.

Associate Editor: Giancarlo Della Ventura

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