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High-temperature behaviour of fluorcarletonite, KNa4Ca4Si8O18(CO3)4(F,OH)⋅H2O, from the Murun Alkaline Complex, Russia, appraised by experimental and theoretical methods

Published online by Cambridge University Press:  25 September 2024

Ernesto Mesto Open the ORCID record for Ernesto Mesto [Opens in a new window] ,
Maria Lacalamita ,
Ekaterina Kaneva Open the ORCID record for Ekaterina Kaneva [Opens in a new window] ,
Roman Shendrik ,
Alexander Bogdanov ,
Marcello Merli Open the ORCID record for Marcello Merli [Opens in a new window]  and
Emanuela Schingaro
Ernesto Mesto
Affiliation:
Earth and Geoenvironmental Sciences Department, University of Bari Aldo Moro, via E. Orabona 4, I-70125 Bari, Italy
Maria Lacalamita*
Affiliation:
Earth and Geoenvironmental Sciences Department, University of Bari Aldo Moro, via E. Orabona 4, I-70125 Bari, Italy
Ekaterina Kaneva
Affiliation:
Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences, 1a Favorsky Str., 664033 Irkutsk, Russia Sidorov Mineralogical Museum, Irkutsk National Research Technical University, 83 Lermontov Str., 664074 Irkutsk, Russia
Roman Shendrik
Affiliation:
Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences, 1a Favorsky Str., 664033 Irkutsk, Russia
Alexander Bogdanov
Affiliation:
Vinogradov Institute of Geochemistry, Siberian Branch of the Russian Academy of Sciences, 1a Favorsky Str., 664033 Irkutsk, Russia
Marcello Merli
Affiliation:
Earth and Sea Sciences Department, University of Palermo, via V. Archirafi 36, I-90123 Palermo, Italy
Emanuela Schingaro
Affiliation:
Earth and Geoenvironmental Sciences Department, University of Bari Aldo Moro, via E. Orabona 4, I-70125 Bari, Italy
*
*Corresponding author: Maria Lacalamita; Email: maria.lacalamita@uniba.it
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Abstract

The thermal behaviour of fluorcarletonite, KNa4Ca4Si8O18(CO3)4(F,OH)⋅H2O, from the charoitites of the Severny district at the Malyy Murun massif, Murun complex, NW Aldan Shield, Siberia, Russia, has been investigated in order to understand the temperature-induced changes in the crystal structure of this rare silicate. The study has been carried out combining in situ high-temperature single-crystal X-ray diffraction (T range 25–550°C), ex situ high-temperature Fourier-transform infrared spectroscopy (25–700°C) and ab initio calculations. An increasing trend of lattice parameters and cell volume was observed in the 150–550°C temperature range, when the mineral underwent a progressive dehydration process. At 550°C ~40% water loss was detected. If compared with the fluorcarletonite structure at room temperature, the partially dehydrated fluorcarletonite shows: the same space group (P4/mbm); increased distances between the oxygens of the H2O molecules (O11w and O12w) and their Na-centred octahedral cations (Na1 and Na2, respectively); distortion of the four- and six-member tetrahedral rings of the double silicate layer. The dehydration process mainly involves the oxygen at the O11w site which has a different local environment with respect to the oxygen at the O12w site. At T > 600°C, the complete dehydration is accompanied by deprotonation of the OH groups substituting for the F atoms and by the collapse of the structure when the CO2 is released. The adopted approach allowed definition of the temperature thresholds at which modifications occur in the fluorcarletonite crystal structure when subjected to controlled heating conditions. Our findings contribute to assessment of stability, reactivity and, more generally, the thermal behaviour of sheet silicates with fluorcarletonite-like topology.

Keywords

fluorcarletonitehigh temperaturesingle-crystal X-ray diffractioninfrared spectroscopyab initio calculations

Information

Type
Article
Information
Mineralogical Magazine , Volume 88 , Issue 4 , August 2024 , pp. 493 - 502
Copyright
Copyright © The Author(s), 2024. Published by Cambridge University Press on behalf of The Mineralogical Society of the United Kingdom and Ireland

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Footnotes

Associate Editor: G. Diego Gatta

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