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The complex mechanism of Ti4+ incorporation into litidionite from the Somma–Vesuvius volcano, Italy

Published online by Cambridge University Press:  16 February 2022

Giuseppina Balassone ,
Taras L. Panikorovskii Open the ORCID record for Taras L. Panikorovskii [Opens in a new window] ,
Annamaria Pellino ,
Ayya V. Bazai ,
Vladimir N. Bocharov Open the ORCID record for Vladimir N. Bocharov [Opens in a new window] ,
Sergey V. Krivovichev ,
Carmela Petti ,
Piergiulio Cappelletti  and
Nicola Mondillo
Giuseppina Balassone
Affiliation:
Department of Earth Science, Environment and Resources (DiSTAR), University of Naples Federico II, Via Cintia, 26, Naples I-80126, Italy National Institute of Geophysics and Volcanology (INGV), Vesuvius Observatory, Via Diocleziano I-80124 Naples, Italy
Taras L. Panikorovskii*
Affiliation:
Kola Science Centre, Russian Academy of Sciences, 14 Fersman Street, Apatity 184200, Russia Department of Crystallography, St. Petersburg State University, 7–9 Universitetskaya, Naberezhnaya, St. Petersburg 199034, Russia
Annamaria Pellino
Affiliation:
Department of Earth Science, Environment and Resources (DiSTAR), University of Naples Federico II, Via Cintia, 26, Naples I-80126, Italy
Ayya V. Bazai
Affiliation:
Kola Science Centre, Russian Academy of Sciences, 14 Fersman Street, Apatity 184200, Russia
Vladimir N. Bocharov
Affiliation:
Geo Environmental Centre “Geomodel”, Saint-Petersburg State University, Ul'yanovskaya Str. 1, St. Petersburg 198504, Russia
Sergey V. Krivovichev
Affiliation:
Kola Science Centre, Russian Academy of Sciences, 14 Fersman Street, Apatity 184200, Russia Department of Crystallography, St. Petersburg State University, 7–9 Universitetskaya, Naberezhnaya, St. Petersburg 199034, Russia
Carmela Petti
Affiliation:
Mineralogical Museum, Centre of Natural Sciences Museums, University of Naples Federico II, Via Mezzocannone 8, Naples I-80134, Italy
Piergiulio Cappelletti
Affiliation:
Department of Earth Science, Environment and Resources (DiSTAR), University of Naples Federico II, Via Cintia, 26, Naples I-80126, Italy Mineralogical Museum, Centre of Natural Sciences Museums, University of Naples Federico II, Via Mezzocannone 8, Naples I-80134, Italy
Nicola Mondillo
Affiliation:
Department of Earth Science, Environment and Resources (DiSTAR), University of Naples Federico II, Via Cintia, 26, Naples I-80126, Italy Department of Earth Sciences, Natural History Museum, London, UK
*
*Author for correspondence: Taras L. Panikorovskii, Email: [email protected]
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Abstract

For this study, the rare Cu-bearing silicate fumarolic assemblages from the Somma–Vesuvius volcano, Italy, characterised by the rare mineral litidionite, CuKNaSi4O10, were investigated. We report new data about Cu- and Ti-bearing phases found in these mineralisations, in which Ti-bearing litidionite occurs together with kamenevite, perovskite and rutile. Ti-bearing litidionite appears on the latest stages of partial crystallisation of Ti-bearing silica glass. Incorporation of Ti4+ into the litidionite crystal structure was investigated in detail. The Raman spectra of Ti-bearing litidionite contains an intense band at 597 cm−1 related to anti-symmetric bending vibrations of Si‒O bonds or overlapping stretching vibrations of Ti‒O bonds. The bands in the range 350‒500 cm−1 correspond to symmetric bending vibrations of O‒Si‒O bonds and overlapping stretching vibrations of Ti‒O bonds. The crystal structure of Ti-litidionite has been refined in the P$\bar{1}$ space group, a = 6.9699(7), b = 7.9953(10), c = 9.8227(10) Å, α = 105.186(9), β = 99.458(8) and γ = 114.489(10) to R1 = 0.064 for 1726 unique observed reflections. The refinement of the site-occupation factors confirmed the presence of Ti at a five-coordinated M site. The mean bond distance of 2.125 Å for the M site agrees with its refined occupancy (Ti0.32Cu0.30Ca0.29Fe0.09)1.00. The incorporation of Ti into the litidionite structure is accompanied by the complex heteropolyhedral substitution according to the scheme VTi4+ + VII–VIII□ + IVAl3+ ↔ VCu2+ + VII-VIII(Na,K)+ + IVSi4+. Two possible configurations for the phase with maximal TiO2 content (12.06 wt.% or 0.56 Ti apfu) CuTiK□Na2Si7AlO20 (Z = 1) or CuTiK2Na□Si7AlO20 (Z = 1) have been proposed.

Keywords

Ti-litidioniteSomma–VesuviusTi incorporationcrystal structure
Type
Article
Information
Mineralogical Magazine , Volume 86 , Issue 2 , April 2022 , pp. 222 - 233
Copyright
Copyright © The Author(s), 2022. Published by Cambridge University Press on behalf of The Mineralogical Society of Great Britain and Ireland

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Footnotes

Associate Editor: G. Diego Gatta

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