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Crystal chemistry of ivanyukite-group minerals, A3–xH1+x[Ti4O4(SiO4)3](H2O)n (A = Na, K, Cu), (n = 6–9, x = 0–2): crystal structures, ion-exchange, chemical evolution

Published online by Cambridge University Press:  07 June 2021

Taras L. Panikorovskii Open the ORCID record for Taras L. Panikorovskii [Opens in a new window] ,
Victor N. Yakovenchuk ,
Nataliya Yu. Yanicheva ,
Yakov A. Pakhomovsky ,
Vladimir V. Shilovskikh ,
Vladimir N. Bocharov  and
Sergey V. Krivovichev
Taras L. Panikorovskii*
Affiliation:
Kola Science Centre, Russian Academy of Sciences, 14 Fersman Street, Apatity184200, Russia Department of Crystallography, St. Petersburg State University, 7–9 University Emb, St. Petersburg199034, Russia
Victor N. Yakovenchuk
Affiliation:
Kola Science Centre, Russian Academy of Sciences, 14 Fersman Street, Apatity184200, Russia
Nataliya Yu. Yanicheva
Affiliation:
Kola Science Centre, Russian Academy of Sciences, 14 Fersman Street, Apatity184200, Russia
Yakov A. Pakhomovsky
Affiliation:
Kola Science Centre, Russian Academy of Sciences, 14 Fersman Street, Apatity184200, Russia
Vladimir V. Shilovskikh
Affiliation:
Geo Environmental Centre “Geomodel”, St. Petersburg State University, Ul'yanovskaya Str., St. Petersburg198504, Russia
Vladimir N. Bocharov
Affiliation:
Geo Environmental Centre “Geomodel”, St. Petersburg State University, Ul'yanovskaya Str., St. Petersburg198504, Russia
Sergey V. Krivovichev
Affiliation:
Kola Science Centre, Russian Academy of Sciences, 14 Fersman Street, Apatity184200, Russia Department of Crystallography, St. Petersburg State University, 7–9 University Emb, St. Petersburg199034, Russia
*
*Author for correspondence: Taras L. Panikorovskii, Email: t.panikorovskii@ksc.ru
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Abstract

Microporous slicates with the pharmacosiderite structure and the general formula A3–xH1+x[Ti4O4(SiO4)3](H2O)n (A = Na, K, Cu), (n = 6–9, x = 0–2) are outstanding in their ion-exchange properties. The ivanyukite mineral group consists of three species, one of which has two polymorphs. The minerals forming a progressive series: ivanyukite-Na-T → ivanyukite-Na-C → ivanyukite-K → Cu-rich ivanyukite-K → ivanyukite-Cu, have been studied by single-crystal X-ray diffraction, electron microprobe analysis and Raman spectroscopy. The microporous heteropolyhedral framework of the ivanyukite-group minerals is based on cubane-like [Ti4O4]8+ clusters that share common corners with SiO4 tetrahedra to form wide three-dimensional channels suitable for the migration of Na+, K+ and Cu2+ ions. Ivanyukite-Na-T that has a R3m symmetry loses Na+ in aqueous solutions via the substitution Na+ + O2‒ ↔ □ + OH‒, which allows for the migration of K+ ions and transformation of initial structure into the cubic (P$\bar{4}3m$) ivanyukite-Na-C polymorph or into ivanyukite-K, when most of Na is lost. Natural ivanyukite-Na-C is shown to contain domains of both R3m (subordinate) and P$\bar{4}3m$ (dominant) symmetry with the chemical composition determining the stability and dominance of cubic or trigonal forms. Incorporation of Cu into the crystal structure ivanyukite-K via the substitution K+ + OH− ↔ Cu2+ + O2− in aqueous solutions results in the formation of ivanyukite-Cu. Post-crystallisation processes (such as exchange of Na+, K+, Cu2+, and/or hydration/dehydration of primary phases) are widespread in hyperagpaitic rocks of the Kola alkaline massif and the respective mineral transformations contribute to the diversity of mineral species.

Keywords

ivanyukite-Na-Tivanyukite-Na-Civanyukite-Kivanyukite-Cupharmacosideriteion-exchangealkaline massifKhibinyArctic
Type
Article – Gregory Yu. Ivanyuk memorial issue
Information
Mineralogical Magazine , Volume 85 , Issue 4 , August 2021 , pp. 607 - 619
Copyright
Copyright © The Author(s), 2021. Published by Cambridge University Press on behalf of The Mineralogical Society of Great Britain and Ireland

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Footnotes

This paper is part of a thematic set ‘Alkaline Rocks’ in memory of Dr Gregory Yu. Ivanyuk

Associate Editor: Elena Zhitova

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