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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

Information

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

References

Arnold, H., Kurtz, W., Richter-Zinnius, A. and Bethke, J. (1981) The phase transition of K2SO4 at about 850 K. Acta Crystallographica, B37, 1643–1651.CrossRefGoogle Scholar
Britvin, S.N., Dolivo-Dobrovolsky, D.V. and Krzhizhanovskaya, M.G. (2017) Software for processing the X-ray powder diffraction data obtained from the curved image plate detector of Rigaku RAXIS Rapid II diffractometer. Proceedings of the Russian Mineralogical Society, 146, 104–107 [in Russian].Google Scholar
Chukanov, N.V., Aksenov, S.M., Rastsvetaeva, R.K., Pekov, I.V., Belakovskiy, D.I. and Britvin, S.N. (2015) Möhnite, (NH4)K2Na(SO4)2, a new guano mineral from Pabellón de Pica, Chile. Mineralogy and Petrology, 109, 643–648.CrossRefGoogle Scholar
Cruickshank, D.W. (1956) Errors in bond lengths due to rotational oscillations of molecules. Acta Crystallographica, 9, 757–758.CrossRefGoogle Scholar
Cruickshank, D.W. (1961) Coordinate errors due to rotational oscillations of molecules. Acta Crystallographica, 14, 896–897.CrossRefGoogle Scholar
Dolivo-Dobrovolsky, V.V. (1984) The crystallography of the Earth's spheres. Proceedings of the Russian Mineralogical Society, 113, 586–590 [in Russian].Google Scholar
Filatov, S.K., Karpov, G.A., Shablinskii, A.P., Krivovichev, S.V., Vergasova, L.P. and Antonov, A.V. (2013) Ivsite, Na3H(SO4)2, a new mineral from volcanic exhalations of fumaroles of the fissure Tolbachik eruption of the 50th anniversary of the Institute of Volcanology and Seismology, Far East Branch, Russian Academy of Sciences. Doklady Earth Sciences, 468, 632–635.CrossRefGoogle Scholar
Filatov, S.K., Shablinskii, A.P., Vergasova, L.P., Saprikina, O.U, Bubnova, R.S, Moskaleva, S.V. and Belousov, A.B. (2019) Belomarinaite KNa(SO4): a new sulfate from 2012–2013 Tolbachik Fissure eruption, Kamchatka Peninsula, Russia. Mineralogical Magazine, 83, 569–575.CrossRefGoogle Scholar
Filatov, S.K., Shablinskii, A.P., Krivovichev, S.V., Vergasova, L.P., and Moskaleva, S.V. (2020) Petrovite, Na10CaCu2(SO4)8, a new fumarolic sulfate from the Great Tolbachik fissure eruption, Kamchatka Peninsula, Russia. Mineralogical Magazine, 84, 691–698.CrossRefGoogle Scholar
Gorelova, L.A., Vergasova, L.P., Krivovichev, S.V., Avdontseva, E.Yu., Moskaleva, S.V., Karpov, G.A. and Filatov, S.K. (2016) Bubnovaite, K2Na8Ca(SO4)6, a new mineral species with modular structure from the Tolbachik volcano, Kamchatka peninsula, Russia. European Journal of Mineralogy, 28, 677–686.CrossRefGoogle Scholar
Hawthorne, F.C., Krivovichev, S.V. and Burns, P.C. (2000) The crystal chemistry of sulfate minerals. Reviews in Mineralogy and Geochemistry, 40, 1–112.CrossRefGoogle Scholar
Kato, E. and Diamon, K. (1979) Crystal structure of anhydrous aluminium sulfate. Journal of the Ceramic Society of Japan, 87, 590–595.Google Scholar
Kato, K. and Saalfeld, H. (1972) The crystal structure of hanksite, KNa22(Cl(CO3)2(SO4)9) and its relation to the K2SO4 I structure type. Acta Crystallographica, B28, 3614–3617.CrossRefGoogle Scholar
Kostov-Kytin, V., Nikolova, R., Kerestedjian, T. and Bezdicka, P. (2013) Temperature-induced phase transformations of the “glaserite” type zirconosilicate Na3HZrSi2O8⋅0.4H2O. Materials Research Bulletin, 48, 2029–2033.CrossRefGoogle Scholar
Krivovichev, S.V. (2012) Topological complexity of crystal structures: quantitative approach. Acta Crystallographica, A68, 393–398.CrossRefGoogle Scholar
Krivovichev, S.V. (2013) Structural complexity of minerals: information storage and processing in the mineral world. Mineralogical Magazine, 77, 275–326.CrossRefGoogle Scholar
Krivovichev, S.V. (2017) Structure description, interpretation and classification in structural mineralogy. Crystallography Reviews, 23, 2–71.CrossRefGoogle Scholar
Krivovichev, S.V. and Filatov, S.K. (1999) Metal arrays in structural units based on anion-centered metal tetrahedral. Acta Crystallographica, B55, 664–676.CrossRefGoogle Scholar
Mandarino, J.A. (1981) The Gladstone–Dale relationship. IV. The compatibility concept and its application. The Canadian Mineralogist, 19, 441–450.Google Scholar
Masse, R., Guitel, J.C. and Perret, R. (1973) Structure cristalline de la variete rhombohedrique du sulfate ferrique Fe2(SO4)3. Bulletin de la Societe Francaise de Mineralogie et de Cristallographie, 96, 346–349.Google Scholar
Okada, K. and Ossaka, J. (1980) Structures of potassium sodium sulphate and tripotassium sodium disulphate. Acta Crystallographica, B36, 919–921.10.1107/S0567740880004852CrossRefGoogle Scholar
O'Keeffe, M. and Hyde, B.G. (1985) An alternative approach to crystal structures with emphasis on the arrangements of cations. Structure and Bonding, 61, 77–144.Google Scholar
Pekov, I.V., Zubkova, N.V., Yapaskurt, V.O., Belakovskiy, D.I., Chukanov, N.V., Lykova, I.S., Savelyev, D.P., Sidorov, E.G. and Pushcharovsky, D.Yu. (2014) Wulffite, K3NaCu4O2(SO4)4, and parawulffite, K5Na3Cu8O4(SO4)8, two new minerals from fumarole sublimates of the Tolbachik volcano, Kamchatka, Russia. The Canadian Mineralogist, 52, 699–716.CrossRefGoogle Scholar
Pekov, I.V., Zubkova, N.V., Agakhanov, A.A., Pushcharovsky, D.Y., Yapaskurt, V.O., Belakovskiy, D.I., Vigasina, M.F., Sidorov, E.G. and Britvin, S.N. (2018) Cryptochalcite, K2Cu5O(SO4)5, and cesiodymite, CsKCu5O(SO4)5, two new isotypic minerals and the K–Cs isomorphism in this solid-solution series. European Journal of Mineralogy, 30, 593–607.CrossRefGoogle Scholar
Pekov, I.V., Shchipalkina, N.V., Zubkova, N.V., Gurzhiy, V.V., Agakhanov, A.A., Belakovskiy Chukanov, N.V., Lykova, I.S., D.I., Vigasina, M.F., Koshlyakova, N.N., Sidorov, E.G. and Giester, G. (2019) Alkali sulfates with aphthitalite-like structures from fumaroles of the Tolbachik volcano, Kamchatka, Russia. I. Metathénardite, a natural high-temperature modification of Na2SO4. The Canadian Mineralogist, 57, 885–901.CrossRefGoogle Scholar
Pekov, I.V., Agakhanov, A.A., Zubkova, N.V., Koshlyakova, N.N., Shchipalkina, N.V., Sandalov, F.D., Yapaskurt, V.O., Turchkova, A.G. and Sidorov, E.G. (2020) Oxidizing-type fumarolic systems of the Tolbachik volcano – a mineralogical and geochemical unique. Russian Geology and Geophysics, 61, 675–688.CrossRefGoogle Scholar
Petříček, V., Dusek, M. and Palatinus, L. (2006) Jana2006. The Crystallographic Computing System. Institute of Physics, Academy of Sciences of the Czech Republic, Prague.Google Scholar
Shablinskii, A.P., Filatov, S.K., Vergasova, L.P., Moskaleva, S.V., Avdontseva, E.Y. and Bubnova, R.S. (2020) Dobrovolskyite, IMA 2019-106. CNMNC Newsletter No. 54; Mineralogical Magazine, 84, 359–365.Google Scholar
Shchipalkina, N.V., Pekov, I.V., Chukanov, N.V., Zubkova, N.V., Belakovskiy, D.I., Koshlyakova, N.N., Britvin, S.N., Sidorov, E.G. and Vozchikova, S.A. (2020) Alkali sulfates with aphthitalite-like structures from fumaroles of the Tolbachik volcano, Kamchatka, Russia. II A new mineral, natroaphthitalite, and new data on belomarinaite. The Canadian Mineralogist, 58, 167–181.CrossRefGoogle Scholar
Siidra, O.I., Nazarchuk, E.V., Zaitsev, A.N. and Vlasenko, N.S. (2020) Koryakite, NaKMg2Al2(SO4)6, a new NASICON-related anhydrous sulfate mineral from Tolbachik volcano, Kamchatka, Russia. Mineralogical Magazine, 84, 283–287.CrossRefGoogle Scholar
Vegas, A. (2000) Cations in inorganic solids. Crystallography Reviews, 7, 189–283.CrossRefGoogle Scholar
Vergasova, L.P. and Filatov, S.K. (2012) New mineral species in products of fumarole activity of Great Tolbachik fissure eruption. Journal of Volcanology and Seismology, 6, 281–289.CrossRefGoogle Scholar
Vergasova, L.P. and Filatov, S.K. (2016) A study of volcanogenic exhalation mineralization. Journal of Volcanology and Seismology, 10, 71–85.CrossRefGoogle Scholar
Vlasse, M., Parent, C., Salmon, R., Le Flem, G. and Hagenmuller, P. (1980) The structures of the Na3Ln(XO4)2 phases (Ln = rare earth, X = P, V, As). Journal of Solid State Chemistry, 35, 318–324.CrossRefGoogle Scholar
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