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Unique thallium mineralization in the fumaroles of Tolbachik volcano, Kamchatka Peninsula, Russia. I. Markhininite, TlBi(SO4)2

Published online by Cambridge University Press:  05 July 2018

Oleg I. Siidra*
Affiliation:
Department of Crystallography, St Petersburg State University, University Emb. 7/9, 199034 St Petersburg, Russia
Lidiya P. Vergasova
Affiliation:
Institute of Volcanology, Russian Academy of Sciences, Bulvar Piypa 9, 683006 Petropavlovsk-Kamchatskiy, Russia
Sergey V. Krivovichev
Affiliation:
Department of Crystallography, St Petersburg State University, University Emb. 7/9, 199034 St Petersburg, Russia Institute of silicate Chemistry, Russian Academy of Sciences, Makarova Emb. 6, 199034 St Petersburg, Russia
Yuri L. Kretser
Affiliation:
V.G. Khlopin Radium Institute, Roentgen Street 1, 197101 St Petersburg, Russia
Anatoly N. Zaitsev
Affiliation:
Department of Mineralogy, St Petersburg State University, University Emb. 7/9, 199034 St Petersburg, Russia
Stanislav K. Filatov
Affiliation:
Department of Crystallography, St Petersburg State University, University Emb. 7/9, 199034 St Petersburg, Russia
*

Abstract

Markhininite, ideally TlBi(SO4)2, was found in a fumarole of the 1st cinder cone of the North Breach of the Great Fissure Tolbachik volcano eruption (1975–1976), Kamchatka Peninsula, Russia. Markhininite occurs as white pseudohexagonal plates associated with shcherbinaite, pauflerite, bobjonesite, karpovite, evdokimovite and microcrystalline Mg, Al, Fe and Na sulfates. Markhininite is triclinic, P, a = 7.378(3), b = 10.657(3), c = 10.657(3) Å , α = 61.31(3), β = 70.964(7), γ = 70.964(7)º, V = 680.2(4) Å3, Z = 4 (from single-crystal diffraction data). The eight strongest lines of the X-ray powder diffraction pattern are (I/d/hkl): 68/4.264/111, 100/3.441/113, 35/3.350/222, 24/3.125/122, 23/3.054/202, 45/2.717/022, 20/2.217/331, 34/2.114/204. Chemical composition determined by electron microprobe analysis is (wt.%): Tl2O 35.41, Bi2O3 38.91, SO3 25.19, total 99.51. The empirical formula based on 8 O a.p.f.u. is Tl1.04Bi1.05S1.97O8. The simplified formula is TlBi(SO4)2, which requires Tl2O 35.08, Bi2O3 38.48, SO3 26.44, total 100.00 wt.%. The crystal structure was solved by direct methods and refined to R1 = 0.055 on the basis of 1425 independent observed reflections. The structure contains four Tl+ and two Bi3+ sites in holodirected symmetrical coordination. BiO8 tetragonal antiprisms and SO4 tetrahedra in markhininite share common O atoms to produce [Bi(SO4)2] layers of the yavapaiite type. The layers are parallel to (111) and linked together through interlayer Tl+ cations. The mineral is named in honour of Professor Yevgeniy Konstantinovich Markhinin (b. 1926), Institute of Volcanology, Russian Academy of Sciences, Kamchatka peninsula, Russia, in recognition of his contributions to volcanology. Markhininite is the first oxysalt compound that contains both Tl and Bi in an ordered crystal structure.

Type
Research Article
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2014

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