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Unique thallium mineralization in the fumaroles of Tolbachik volcano, Kamchatka Peninsula, Russia. III. Evdokimovite, Tl4(VO)3(SO4)5(H2O)5

Published online by Cambridge University Press:  05 July 2018

Oleg I. Siidra ,
Lidiya P. Vergasova ,
Yuri L. Kretser ,
Yuri S. Polekhovsky ,
Stanislav K. Filatov  and
Sergey V. Krivovichev
Oleg I. Siidra*
Affiliation:
Department of Crystallography, St Petersburg State University, University Embankment 7/9, 199034 St Petersburg, Russia
Lidiya P. Vergasova
Affiliation:
Institute of Volcanology, Russian Academy of Sciences, Bulvar Piypa 9, 683006 Petropavlovsk-Kamchatskiy, Russia
Yuri L. Kretser
Affiliation:
V.G. Khlopin Radium Institute, Roentgen Street 1, 197101 St Petersburg, Russia
Yuri S. Polekhovsky
Affiliation:
Department of Mineral Deposits, St Petersburg State University, University Embankment 7/9, 199034 St Petersburg, Russia
Stanislav K. Filatov
Affiliation:
Department of Crystallography, St Petersburg State University, University Embankment 7/9, 199034 St Petersburg, Russia
Sergey V. Krivovichev
Affiliation:
Department of Crystallography, St Petersburg State University, University Embankment 7/9, 199034 St Petersburg, Russia Institute of Silicate Chemistry, Russian Academy of Sciences, Makarova Emb. 6, 199034 St Petersburg, Russia
*
* E-mail: o.siidra@spbu.ru
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Abstract

Evdokimovite, ideally Tl4(VO)3(SO4)5(H2O)5, was found in a fumarole of the 1st cinder cone of the North Breach of the Great Fissure Tolbachik volcano eruption of 1975–1976, Kamchatka Peninsula, Russia. Evdokimovite occurs as thin, colourless needles up to 0.09 mm long associated with shcherbinaite, pauflerite, bobjonesite, markhininite, karpovite and microcrystalline Mg, Al, Fe and Na sulfates. Evdokimovite is monoclinic, P21/n, a = 6.2958(14), b = 10.110(2), c = 39.426(11) Å , β = 90.347(6)º, V = 2509.4(10) Å3 and Z = 4 (from single-crystal diffraction data). The eight strongest lines of the powder X-ray diffraction pattern are (I/d/hkl): 57/9.793/011, 100/8.014/013, 26/6.580/006, 19/ 4.011/026, 29/3.621/118, 44/3.522/125, 19/3.010/036, 21/2.974/212. Chemical composition determined by the electron microprobe analysis is (wt.%): Tl2O 55.40, VO2 14.92, SO3 25.83, H2O 5.75, total 101.90. The empirical formula for evdokimovite calculated on the basis of (Tl + V + S) = 12 a.p.f.u. is Tl4.10V2.83S5.07H10.00O27.94. The simplified formula is Tl4(VO)3(SO4)5(H2O)5. The crystal structure was solved by direct methods and refined to R1 = 0.11 on the basis of 3660 independent observed reflections. V4+O6 octahedra and SO4 tetrahedra share common corners to form two types of vanadyl-sulfate chains, [(VO)(H2O)2(SO4)2]2– and [(VO)2(H2O)3(SO4)3]2–. Thallium atoms are located in between the chains. The structure can be described as a stacking of layers of two types, A and B. The A layer contains [(VO)2(H2O)3(SO4)3]2– chains and the Tl2 and Tl3 atoms, whereas the B layer contains [(VO)(H2O)2(SO4)2]2– chains and the Tl1 atoms. Stacking of the layers can be described as ...A’*BAA’B*A*..., where A and A’ denote A layers with opposite orientations of the [(VO)2(H2O)3(SO4)3]2– chains, and the A* and B* layers are rotated by 180º relative to the A and B layers, respectively. [(VO)2(H2O)3(SO4)3]2– chains are modulated and are arranged to form elliptical tunnels hosting disordered Tl(4), Tl(4A) and Tl(4B) sites. The new mineral is named in honour of Professor Mikhail Dmitrievich Evdokimov (1940–2010), formerly of the Department of Mineralogy, St Petersburg State University, for his contributions to mineralogy and petrology, and especially for teaching mineralogy to several generations of students at the University. Evdokimovite is the most complex V4+ sulfate known to date with structural information amounting to 1130 bits per unit cell, which places evdokimovite among minerals with the complexity of the vesuvianite group.

Keywords

evdokimovitenew mineralthalliumvanadiumvanadyl ionsulfatelone electron pairTolbachik volcanostructural complexity
Type
Research Article
Information
Mineralogical Magazine , Volume 78 , Issue 7 , December 2014 , pp. 1711 - 1724
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2014

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