TY - JOUR

T1 - A fumarole in a one-pot

T2 - synthesis, crystal structure and properties of Zn- and Mg-analogs of itelmenite and a synthetic analog of glikinite

AU - Nekrasova, Diana O.

AU - Siidra, Oleg I.

AU - Zaitsev, Anatoly N.

AU - Ugolkov, Valery L.

AU - Colmont, Marie

AU - Charkin, Dmitry O.

AU - Mentré, Olivier

AU - Chen, Ruiqi

AU - Kovrugin, Vadim M.

AU - Borisov, Artem S.

N1 - Funding Information: We are grateful to Ton?i Bali?-?uni?, Wulf Depmeier and an anonymous reviewer for valuable comments. This work was financially supported by the Russian Science Foundation through the grant 16-17-10085. Technical support by the SPbSU X-ray Diffraction and Geomodel Resource Centers is gratefully acknowledged. The Chevreul Institute (FR 2638), the Minist?re de l?Enseignement Sup?rieur et de la Recherche, the R?gion Hauts-de-France, the CNRS, and the FEDER are acknowledged for supporting and funding this work. Funding Information: We are grateful to Tonči Balić-Žunić, Wulf Depmeier and an anonymous reviewer for valuable comments. This work was financially supported by the Russian Science Foundation through the grant 16-17-10085. Technical support by the SPbSU X-ray Diffraction and Geomodel Resource Centers is gratefully acknowledged. The Chevreul Institute (FR 2638), the Ministère de l’Enseignement Supérieur et de la Recherche, the Région Hauts-de-France, the CNRS, and the FEDER are acknowledged for supporting and funding this work. Publisher Copyright: © 2021, The Author(s), under exclusive licence to Springer-Verlag GmbH, DE part of Springer Nature. Copyright: Copyright 2021 Elsevier B.V., All rights reserved.

PY - 2021/1/11

Y1 - 2021/1/11

N2 - Anhydrous sulfate minerals are abundant in the active fumaroles with highly oxidizing conditions on the scoria cones of the Tolbachik volcano. The mineral itelmenite, ideally Na2CuMg2(SO4)4, containing isomorphous admixture of Zn, was described in 2018, whereas glikinite, ideally Zn3O(SO4)2, was described in 2020. Synthetic analogs of both minerals were obtained during studies of phase formation in the Na2SO4–CuSO4–MgSO4–(ZnSO4) systems which lead to essentially different results. Solid-state syntheses resulted in formation of several compounds previously known as minerals only. Both Zn- and Mg-containing analogs of itelmenite were prepared and exhibit slight deviations from the ideal Na2CuM2(SO4)4 stoichiometry. The Mg compound could be prepared single-phase which allowed the study of its thermal expansion and IR spectroscopy. Na2CuMg2(SO4)4 and Na2CuZn2(SO4)4 were evaluated for Na+-ion diffusion. For the Zn compound, several by-products were observed which are synthetic analogs of puninite Na2Cu3O(SO4)2, as well as hermannjahnite CuZn(SO4)2 and glikinite-type (Zn,Cu)3O(SO4)2. All of them were prepared via solid-state reactions in open systems. The Na2CuMg2(SO4)4, Na2CuZn2(SO4)4 and (Zn,Cu)3O(SO4)2 were structurally characterized by the single-crystal XRD. In the Zn-bearing system, the admixture of Cu2+ likely controls the formation of itelmenite-type and glikinite-type phases. The results of the experiments allowed to deduce possible scenarios of the formation processes of itelmenite and some other endemic fumarolic minerals. Our study shows that outstanding mineralogical diversity observed in the fumaroles of the Tolbachik scoria cones is not only due to the formation from the gas enriched by transition metals and involves also intensive exchange with the host basaltic scoria. Similar processes seem also to be responsible for the recrystallization of many other mineral species observed in high-temperature fumaroles resulted from the recent eruptions.

AB - Anhydrous sulfate minerals are abundant in the active fumaroles with highly oxidizing conditions on the scoria cones of the Tolbachik volcano. The mineral itelmenite, ideally Na2CuMg2(SO4)4, containing isomorphous admixture of Zn, was described in 2018, whereas glikinite, ideally Zn3O(SO4)2, was described in 2020. Synthetic analogs of both minerals were obtained during studies of phase formation in the Na2SO4–CuSO4–MgSO4–(ZnSO4) systems which lead to essentially different results. Solid-state syntheses resulted in formation of several compounds previously known as minerals only. Both Zn- and Mg-containing analogs of itelmenite were prepared and exhibit slight deviations from the ideal Na2CuM2(SO4)4 stoichiometry. The Mg compound could be prepared single-phase which allowed the study of its thermal expansion and IR spectroscopy. Na2CuMg2(SO4)4 and Na2CuZn2(SO4)4 were evaluated for Na+-ion diffusion. For the Zn compound, several by-products were observed which are synthetic analogs of puninite Na2Cu3O(SO4)2, as well as hermannjahnite CuZn(SO4)2 and glikinite-type (Zn,Cu)3O(SO4)2. All of them were prepared via solid-state reactions in open systems. The Na2CuMg2(SO4)4, Na2CuZn2(SO4)4 and (Zn,Cu)3O(SO4)2 were structurally characterized by the single-crystal XRD. In the Zn-bearing system, the admixture of Cu2+ likely controls the formation of itelmenite-type and glikinite-type phases. The results of the experiments allowed to deduce possible scenarios of the formation processes of itelmenite and some other endemic fumarolic minerals. Our study shows that outstanding mineralogical diversity observed in the fumaroles of the Tolbachik scoria cones is not only due to the formation from the gas enriched by transition metals and involves also intensive exchange with the host basaltic scoria. Similar processes seem also to be responsible for the recrystallization of many other mineral species observed in high-temperature fumaroles resulted from the recent eruptions.

KW - Anhydrous sulfates

KW - Framework structures

KW - Fumarolic mineral assemblages

KW - Glikinite

KW - Hermannjahnite

KW - Itelmenite

KW - MgSO

KW - Puninite

KW - Solid-state reactions

KW - X-ray diffraction

KW - ZnSO

UR - http://www.scopus.com/inward/record.url?scp=85099198085&partnerID=8YFLogxK

U2 - 10.1007/s00269-020-01132-4

DO - 10.1007/s00269-020-01132-4

M3 - Article

AN - SCOPUS:85099198085

VL - 48

JO - Physics and Chemistry of Minerals

JF - Physics and Chemistry of Minerals

SN - 0342-1791

IS - 1

M1 - 6

ER -