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Calciolangbeinite-O, a natural orthorhombic modification of K2Ca2(SO4)3, and the langbeinite–calciolangbeinite solid-solution system

Published online by Cambridge University Press:  28 January 2022

Igor V. Pekov*
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991 Moscow, Russia
Natalia V. Zubkova
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991 Moscow, Russia
Irina O. Galuskina
Faculty of Natural Sciences, University of Silesia, Będzińska 60, 41-200 Sosnowiec, Poland
Joachim Kusz
Faculty of Science and Technology, University of Silesia, ul. 75. Pułku Piechoty 1, 41-500 Chorzów, Poland
Natalia N. Koshlyakova
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991 Moscow, Russia
Evgeny V. Galuskin
Faculty of Natural Sciences, University of Silesia, Będzińska 60, 41-200 Sosnowiec, Poland
Dmitry I. Belakovskiy
Fersman Mineralogical Museum of the Russian Academy of Sciences, Leninsky Prospekt 18-2, 119071 Moscow, Russia
Maria O. Bulakh
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991 Moscow, Russia
Marina F. Vigasina
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991 Moscow, Russia
Nikita V. Chukanov
Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka, Moscow Oblast, Russia
Sergey N. Britvin
Dept. of Crystallography, St. Petersburg State University, University Emb. 7/9, 199034 St. Petersburg, Russia
Evgeny G. Sidorov
Institute of Volcanology and Seismology, Far Eastern Branch of Russian Academy of Sciences, Piip Boulevard 9, 683006 Petropavlovsk-Kamchatsky, Russia
Yevgeny Vapnik
Department of Geological and Environmental Sciences, Ben-Gurion University of the Negev, POB 653, Beer-Sheva 84105, Israel
Dmitry Yu. Pushcharovsky
Faculty of Geology, Moscow State University, Vorobievy Gory, 119991 Moscow, Russia
*Author for correspondence: Igor V. Pekov, Email:


Calciolangbeinite, ideally K2Ca2(SO4)3, exists in two modifications, cubic and, first described in the present paper, orthorhombic. They are topologically-similar polymorphs which can be designated as calciolangbeinite-C and calciolangbeinite-O. Calciolangbeinite-O is the first natural orthorhombic langbeinite-like sulfate. It clearly differs from calciolangbeinite-C in the powder X-ray diffraction pattern, optical data and Raman spectrum. Calciolangbeinite-O is found in sublimates of the active Arsenatnaya fumarole at the Tolbachik volcano, Kamchatka, Far Eastern Region, Russia and in pyrometamorphic rocks of the Hatrurim Complex at Jabel Harmun, Judean Desert, Palestinian Autonomy and Har Parsa, Negev Desert, both in Israel. Calciolangbeinite-C is known only in fumarole sublimates at Tolbachik. Calciolangbeinite forms a continuous solid-solution system with langbeinite K2Mg2(SO4)3. The majority of the system is represented by cubic phases, and only members with compositions K2(Ca2.0–1.9Mg0.0–0.1)(SO4)3 have orthorhombic symmetry under room-temperature conditions. The crystal structure of calciolangbeinite-O was studied on a single crystal, chemically very close to K2Ca2(SO4)3, from Tolbachik (R1 = 2.75%). The unit-cell parameters are: a = 10.3330(2), b = 10.5027(2), c = 10.1763(2) Å, V = 1104.37(4) Å3 and Z = 4; space group is P212121. Calciolangbeinite-O is a low-temperature modification of K2Ca2(SO4)3 belonging to the K2Cd2(SO4)3 structure type whereas calciolangbeinite-C (space group P213), a high-temperature modification, has the langbeinite-type structure. The significant Mg admixture in calciolangbeinite-C from Tolbachik probably stabilises its cubic structure at room temperature. In both high-temperature fumaroles and pyrometamorphic rocks calciolangbeinite crystallises in the cubic modification, and during cooling its chemical variety close to the end-member K2Ca2(SO4)3 undergoes phase transition to calciolangbeinite-O, whereas the Mg-enriched varieties of the mineral remain calciolangbeinite-C.

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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This paper is part of a thematic set that honours the contributions of Peter Williams

Deceased 20 March 2021

Guest Associate Editor: Clara Magalhães


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