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Dobrovolskyite, Na4Ca(SO4)3, a new fumarolic sulfate from the Great Tolbachik fissure eruption, Kamchatka Peninsula, Russia

Published online by Cambridge University Press:  29 January 2021

Andrey P. Shablinskii Open the ORCID record for Andrey P. Shablinskii [Opens in a new window] ,
Stanislav K. Filatov Open the ORCID record for Stanislav K. Filatov [Opens in a new window] ,
Sergey V. Krivovichev ,
Lidiya P. Vergasova ,
Svetlana V. Moskaleva ,
Eugeniya Yu. Avdontseva ,
Alexander V. Knyazev  and
Rimma S. Bubnova Open the ORCID record for Rimma S. Bubnova [Opens in a new window]
Andrey P. Shablinskii
Affiliation:
Institute of Earth Sciences, Saint Petersburg State University, University Emb. 7/9., 199034, Saint Petersburg, Russia Institute of Silicate Chemistry of the Russian Academy of Sciences, Makarova Emb. 2., 199034, Saint Petersburg, Russia
Stanislav K. Filatov*
Affiliation:
Institute of Earth Sciences, Saint Petersburg State University, University Emb. 7/9., 199034, Saint Petersburg, Russia Faculty of Chemistry, N.I. Lobachevsky State University of Nizhny Novgorod, Prospect Gagarina 23, 603950, Nizhny Novgorod, Russia
Sergey V. Krivovichev
Affiliation:
Institute of Earth Sciences, Saint Petersburg State University, University Emb. 7/9., 199034, Saint Petersburg, Russia Institute of Silicate Chemistry of the Russian Academy of Sciences, Makarova Emb. 2., 199034, Saint Petersburg, Russia Nanomaterials Research Centre, Kola Science Centre of the Russian Academy of Sciences, Fersmana str. 14., 184209, Apatity, Russia
Lidiya P. Vergasova
Affiliation:
Institute of Volcanology and Seismology, Far Eastern Branch of the Russian Academy of Sciences, Piip Boulevard 9, 683006, Petropavlovsk-Kamchatsky, Russia
Svetlana V. Moskaleva
Affiliation:
Institute of Volcanology and Seismology, Far Eastern Branch of the Russian Academy of Sciences, Piip Boulevard 9, 683006, Petropavlovsk-Kamchatsky, Russia
Eugeniya Yu. Avdontseva
Affiliation:
Institute of Earth Sciences, Saint Petersburg State University, University Emb. 7/9., 199034, Saint Petersburg, Russia
Alexander V. Knyazev
Affiliation:
Faculty of Chemistry, N.I. Lobachevsky State University of Nizhny Novgorod, Prospect Gagarina 23, 603950, Nizhny Novgorod, Russia
Rimma S. Bubnova
Affiliation:
Institute of Silicate Chemistry of the Russian Academy of Sciences, Makarova Emb. 2., 199034, Saint Petersburg, Russia
*
*Author for correspondence: Stanislav K. Filatov, Email: filatov.stanislav@gmail.com
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Abstract

Dobrovolskyite, Na4Ca(SO4)3, is a new sulfate mineral from the Great Tolbachik fissure eruption, Kamchatka peninsula, Russia. It occurs as aggregates of tabular crystals up to 1–2 mm in maximum dimension, with abundant gas inclusions. The empirical formula calculated on the basis of O = 12 is (Na3.90K0.10)Σ4(Ca0.45Mg0.16Cu0.12Na0.10)Σ0.83S3.08O12. The crystal structure of dobrovolskyite was determined using single-crystal X-ray diffraction data as: trigonal, R3, a = 15.7223(2), c = 22.0160(5) Å, V = 4713.1(2) Å3, Z = 18 and R1 = 0.072. The Mohs’ hardness is 3.5. The mineral is uniaxial (+), with ω = 1.489(2) and ɛ = 1.491(2) (λ = 589 nm). The seven strongest lines of the powder X-ray diffraction pattern [d, Å (I, %)(hkl)] are: 11.58(40)(101); 5.79(22)(202); 4.54(18)(030); 3.86(88)(033); 3.67(32)(006); 2.855(50)(306); and 2.682(100)(330). The mineral is named in honour of Prof. Dr. Vladimir Vitalievich Dolivo-Dobrovolsky (1927–2009), one of the leading Russian scientists in the field of petrology, crystal optics and crystal chemistry. The crystal structure of dobrovolskyite can be described as composed of three symmetrically independent rods running parallel to the c axis. The rods consist of six octahedral–tetrahedral [Na(SO4)6]11– or [Ca(SO4)6]10– clusters of central octahedra sharing common corners with six adjacent SO4 tetrahedra. Alternatively, the crystal structure of the mineral can be described as a 12-layer ABACABACABAC eutactic array of Na+ and Ca2+ cations, and vacancies with disordered (SO4) tetrahedra in interstices. Dobrovolskyite and similar minerals probably formed upon cooling of a high-temperature phase with disordered cation and anion arrangements.

Keywords

dobrovolskyitenew mineralsulfatecrystal structurefumarolic mineralsTolbachikKamchatka peninsulamodular structureeutactic cation arrays
Type
Article
Information
Mineralogical Magazine , Volume 85 , Issue 2 , April 2021 , pp. 233 - 241
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

Associate Editor: Michael Rumsey

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