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A fumarole in a one-pot: synthesis, crystal structure and properties of Zn- and Mg-analogs of itelmenite and a synthetic analog of glikinite

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Abstract

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.

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References

  • Bald L, Grühn R (1981) Die Kristallstruktur von einem Sulfat-reichen Oxidsulfat des Zinks. Naturwissenschaften 68:39–39

    Article  Google Scholar 

  • Balić Žunić T, Garavelli A, Acquafredda P, Leonardsen E, Jakobsson SP (2009) Eldfellite, a new fumarolic mineral from Eldfell volcano, Iceland. Mineral Mag 73:51–57

    Article  Google Scholar 

  • Barpanda P (2015) Sulfate chemistry for high-voltage insertion materials: synthetic, structural and electrochemical insights. Isr J Chem 55:537–557

    Article  Google Scholar 

  • Barpanda P, Oyama G, Nishimura S, Chung S-C, Yamada A (2014) A 3.8-V earth-abundant sodium battery electrode. Nat Commun 5:4358

    Article  Google Scholar 

  • Belousov A, Belousova M, Edwards B, Volynets A, Melnikov D (2015) Overview of the precursors and dynamics of the 2012–13 basaltic fissure eruption of Tolbachik Volcano, Kamchatka, Russia. J Volcanol Geoth Res 307:22–37

    Article  Google Scholar 

  • Berg RW, Thorup N (2005) The reaction between ZnO and molten Na2S2O7 or K2S2O7 forming Na2Zn(SO4)2 or K2Zn(SO4)2, studied by Raman spectroscopy and X-ray diffraction. Inorg Chem 44:3485–3493

    Article  Google Scholar 

  • Boivin E, Chotard J-N, Ménétrier M, Bourgeois L, Bamine T, Carlier D, Fauth F, Suard E, Masquelier C, Croguennec L (2016) Structural and electrochemical studies of a new Tavorite composition: LiVPO4OH. J Mater Chem A4:11030–11045

    Article  Google Scholar 

  • Boivin E, Chotard J-N, Bamine T, Carlier D, Serras P, Palomares V, Rojo T, Iadecola A, Dupont L, Bourgeois L, Fauth F, Masquelier C, Croguennec L (2017) Vanadyl-type defects in Tavorite-like NaVPO4F: from the average long range structure to local environments. J Mater Chem A5:25044–25055

    Article  Google Scholar 

  • Boucher F, Evain M, Brec R (1994) Second-order Jahn-Teller effect in CdPS3 and ZnPS3 demonstrated by a non-harmonic behaviour of Cd2+ and Zn2+ d10 ions. J Alloy Compd 215:63–70

    Article  Google Scholar 

  • Bruker-AXS (2014) APEX2. Version 2014.11–0. Madison, Wisconsin, USA

  • Chaplygin I, Lavrushin V, Dubinina E, Bychkova YV, Inguaggiato S, Yudovskaya M (2016) Geochemistry of volcanic gas at the 2012–13 New Tolbachik eruption, Kamchatka. J Volcanol Geoth Res 323:186–193

    Article  Google Scholar 

  • Fedotov SA, Markhinin YK (eds) (1983) The Great Tolbachik Fissure Eruption. Cambridge Univ. Press, New York

    Google Scholar 

  • Firsova VA, Bubnova RS, Filatov SK (2011) Program for the thermal expansion tensor determination for crystalline materials. Institute of Silicate Chemistry of Russ. Acad. Sci, St. Petersburg, Russia

    Google Scholar 

  • Halcrow MA (2013) Jahn-Teller distortions in transition metal compounds, and their importance in functional molecular and inorganic materials. Chem Soc Rev 42:1784–1795

    Article  Google Scholar 

  • Katcho NA, Carrete J, Reynaud M, Rousse G, Casas-Cabanas M, Mingo N, Rodríguez-Carvajal J, Carrasco J (2019) An investigation of the structural properties of Li and Na fast ion conductors using high-throughput bond-valence calculations and machine learning. J Appl Cryst 52:148–157

    Article  Google Scholar 

  • Kovrugin VM, David R, Chotard J-N, Recham N, Masquelier C (2018) A high voltage cathode material for sodium batteries: Na3V(PO4)2. Inorg Chem 57:8760–8768

    Article  Google Scholar 

  • Kovrugin VM, Nekrasova DO, Siidra OI, Mentré O, Masquelier C, Stefanovich SY, Colmont M (2019) Mineral-inspired crystal growth and physical properties of Na2Cu(SO4)2 and review of Na2M(SO4)2(H2O)x (x = 0–6) compounds. Cryst Growth Des 19:1233–1244

    Article  Google Scholar 

  • Krivovichev SV, Mentré O, Siidra OI, Colmont M, Filatov SK (2013) Anion-centered tetrahedra in inorganic compounds. Chem Rev 113:6459–6535

    Article  Google Scholar 

  • Lander L, Rousse G, Batuk D, Colin CV, Dalla Corte DA, Tarascon J-M (2017) Synthesis, structure, and electrochemical properties of K-based sulfates K2M2(SO4)3 with M = Fe and Cu. Inorg Chem 56:2013–2021

    Article  Google Scholar 

  • Lander L, Tarascon J-M, Yamada A (2018) Sulfate-based cathode materials for Li- and Na-ion batteries. Chem Rec 18:1394–1408

    Article  Google Scholar 

  • Nazarchuk EV, Siidra OI, Agakhanov AA, Lukina EA, Avdontseva EY, Karpov GA (2018) Itelmenite, Na2CuMg2(SO4)4, a new anhydrous sulphate mineral from the Tolbachik volcano. Mineral Mag 82:1233–1241

    Article  Google Scholar 

  • Nazarchuk EV, Siidra OI, Nekrasova DO, Shilovskikh VV, Borisov AS, Avdontseva EYu (2020) Glikinite, Zn3O(SO4)2, a new anhydrous zinc oxysulphate mineral structurally based on OZn4 tetrahedra. Mineral Mag 84:563–567

    Article  Google Scholar 

  • Pautov LA, Mirakov MA, Siidra OI, Faiziev AR, Nazarchuk EV, Karpenko VYu, Makhmadsharif S (2020) Falgarite, K4(VO)3(SO4)5, a new mineral from sublimates of a natural underground coal fire at the tract of Kukhi-Malik, Fan-Yagnob coal deposit, Tajikistan. Mineral Mag 84:455–462

    Article  Google Scholar 

  • Pekov IV, Koshlyakova NN, Zubkova NV, Lykova IS, Britvin SN, Yapaskurt VO, Agakhanov AA, Shchipalkina NV, Turchkova AG, Sidorov EG (2018a) Fumarolic arsenates - a special type of arsenic mineralization. Eur J Mineral 30:305–322

    Article  Google Scholar 

  • Pekov IV, Zubkova NV, Pushcharovsky DYu (2018b) Copper minerals from volcanic exhalations—a unique family of natural compounds: crystal-chemical review. Acta Crystallogr B 74:502–518

    Article  Google Scholar 

  • Petříček V, Dušek M, Palatinus L (2014) Crystallographic computing system JANA2006: general features. Z Kristallogr Cryst Mater 229:345–352

    Article  Google Scholar 

  • Rodríguez-Carvajal J (1993) Recent advances in magnetic structure determination by neutron powder diffraction. Phys B 192:55–69

    Article  Google Scholar 

  • Secco EA (1988) Spectroscopic properties of SO4 (and OH) in different molecular and crystalline environments. I. Infrared spectra of Cu4(OH)6SO4, Cu4(OH)4OSO4, and Cu3(OH)4SO4. Can J Chem 66:329–336

    Article  Google Scholar 

  • Sharygin VV, Sokol EV, Belakovski DI (2009) Fayalite-sekaninaite paralava from the Ravat coal fire (central Tajikistan). Russ Geol Geophys 50:703–721

    Article  Google Scholar 

  • Shchipalkina NV, Pekov IV, Koshlyakova NN, Britvin SN, Zubkova NV, Varlamov DA, Sidorov EG (2020) Unusual silicate mineralization in fumarolic sublimates of the Tolbachik volcano, Kamchatka, Russia—Part 1: Neso-, cyclo-, ino- and phyllosilicates. Eur J Mineral 32:101–119

    Article  Google Scholar 

  • Sheldrick GM (2015) Crystal structure refinement with SHELXL. Acta Crystalogr C71:3–8

    Google Scholar 

  • Siidra OI, Nazarchuk EV, Zaitsev AN, Lukina EA, Avdontseva EY, Vergasova LP, Vlasenko NS, Filatov SK, Turner R, Karpov GA (2017) Copper oxosulphates from fumaroles of Tolbachik Vulcano: puninite, Na2Cu3O(SO4)3—a new mineral species and structure refinements of kamchatkite and alumoklyuchevskite. Eur J Mineral 29:499–510

    Article  Google Scholar 

  • Siidra OI, Nazarchuk EV, Agakhanov AA, Lukina EA, Zaitsev AN, Turner R, Filatov SK, Pekov IV, Karpov GA, Yapaskurt VO (2018) Hermannjahnite, CuZn(SO4)2, a new mineral with chalcocyanite derivative structure from the Naboko scoria cone of the 2012–2013 fissure eruption at Tolbachik volcano, Kamchatka, Russia. Miner Petrol 112:123–134

    Article  Google Scholar 

  • Siidra OI, Borisov AS, Lukina EA, Depmeier W, Platonova NV, Colmont M, Nekrasova DO (2019) Reversible hydration/dehydration and thermal expansion of euchlorine, ideally KNaCu3O(SO4)3. Phys Chem Miner 46:403–416

    Article  Google Scholar 

  • Singh P, Shiva K, Celio H, Goodenough JB (2015) Eldfellite, NaFe(SO4)2: an intercalation cathode host for low-cost Na-ion batteries. Energ Environ Sci 8:3000–3005

    Article  Google Scholar 

  • Smith DH, Seshadri KS (1999) Infrared spectra of Mg2Ca(SO4)3, MgSO4, hexagonal CaSO4, and orthorhombic CaSO4. Spectrochim Acta A55:795–805

    Article  Google Scholar 

  • Sun M, Rousse G, Abakumov AM, Saubanère M, Doublet M-L, Rodríguez-Carvajal J, Van Tendeloo G, Tarascon J-M (2015) Li2Cu2O(SO4)2: a possible electrode for sustainable Li-based batteries showing a 4.7 V redox activity vs Li+/Li0. Chem Mater 27:3077–3087

    Article  Google Scholar 

  • Vergasova LP, Filatov SK (2012) New mineral species in products of fumarole activity of the Great Tolbachik Fissure Eruption. J Volcanol Seismol 6:281–289

    Article  Google Scholar 

  • Wildner M (1992) On the geometry of Co(II)O6 polyhedra in inorganic compounds. Z Kristallogr 202:51–70

    Article  Google Scholar 

  • Zelenski M, Malik N, Taran NY (2014) Emissions of trace elements during the 2012–2013 effusive eruption of Tolbachik volcano, Kamchatka: enrichment factors, partition coefficients and aerosol contribution. J Volcanol Geotherm Res 285:136–149

    Article  Google Scholar 

Download references

Acknowledgements

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.

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Authors and Affiliations

  1. Department of Crystallography, St. Petersburg State University, University Embankment 7/9, 199034, St. Petersburg, Russia

    Diana O. Nekrasova, Oleg I. Siidra, Ruiqi Chen, Vadim M. Kovrugin & Artem S. Borisov

  2. Université Lille, CNRS, Centrale Lille, Université Artois, UMR 8181, Unité de Catalyse et Chimie du Solide, 59000, Lille, France

    Diana O. Nekrasova, Marie Colmont & Olivier Mentré

  3. Institute of Silicate Chemistry, Russian Academy of Sciences, Makarov Emb. 2, 199034, St. Petersburg, Russia

    Oleg I. Siidra & Valery L. Ugolkov

  4. Department of Mineralogy, St. Petersburg State University, University Embankment 7/9, 199034, St. Petersburg, Russia

    Anatoly N. Zaitsev

  5. Department of Chemistry, Moscow State University, GSP-1, Moscow, 119991, Russia

    Dmitry O. Charkin

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  1. Diana O. Nekrasova
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Nekrasova, D.O., Siidra, O.I., Zaitsev, A.N. et al. A fumarole in a one-pot: synthesis, crystal structure and properties of Zn- and Mg-analogs of itelmenite and a synthetic analog of glikinite. Phys Chem Minerals 48, 6 (2021). https://doi.org/10.1007/s00269-020-01132-4

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