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Gungerite, TlAs5Sb4S13, a new thallium sulfosalt with a complex structure containing covalent As-As bonds

  • Anatoly V. Kasatkin , Jakub Plášil ORCID logo , Emil Makovicky , Nikita V. Chukanov , Radek Škoda , Atali A. Agakhanov and Mikhail V. Tsyganko
Published/Copyright: May 27, 2022
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American Mineralogist
From the journal American Mineralogist Volume 107 Issue 6

Abstract

Gungerite, TlAs5Sb4S13, is a new mineral from the Vorontsovskoye gold deposit in Northern Urals. It occurs in limestone breccias composed of calcite and dolomite and cemented by orpiment, pyrite, realgar, stibnite, and minor baryte and quartz. It belongs to the latest phases among sulfosalts (chiefly Tl-As-Sb ones) present in the ore. The empirical formula (based on the sum of all atoms = 23 pfu) is Tl0.99As5.29Sb3.77S12.95. The Raman spectrum exhibits bands corresponding to As-S and Sb-S stretching vibrations, and a band at 263 cm−1 that is assigned to As–As stretching vibrations. Gungerite is bright orange with an orange streak, greasy luster, and perfect cleavage on {010}. It is translucent in thin fragments. The calculated density is 4.173 g/cm3. In reflected light, the mineral is yellowish-white with very weak bireflectance. In crossed polars, it is distinctly anisotropic but anisotropy efects are masked by strong internal reflections of bright orange color. Gungerite is orthorhombic, with the space group Pbcn. Unit-cell parameters determined from the single-crystal X-ray difraction data are as follows: a = 20.1958(3) Å, b = 11.5258(2) Å, c = 20.1430(2) Å, and V = 4688.74(12) Å3 (Z = 8). The crystal structure consists of doughnut-shaped (As,Sb)-S clusters, which have van der Waals contacts to most of the surroundings, and are connected to them only by sparse cation-sulfur bonds. These clusters are formed by a chelating mirror-symmetrical group, which is “stacked” on, around, and along rods of the TlS9 coordination polyhedra; these rods are oriented parallel to [010]. An individual doughnut-shaped cluster with a central TlS9 polyhedron half-inserted into it contains one As–As bond 2.449 Å long. The polar Tl rods form a chessboard arrangement with occasional stacking errors leading to twinning on (101). The large and complex structure of gungerite shows remote similarities to that of gillulyite and the rod-like structure of lorándite.

Keywords: Gungerite; new mineral species; Tl-As-Sb sulfosalt; Raman spectroscopy; crystal structure; covalent bonds; Vorontsovskoe gold deposit

Acknowledgments and Funding

Three anonymous reviewers and Associate Editor Diego Gatta are thanked for constructive comments, which improved the manuscript. The friendly interest of T. Balić-Žunić and further colleagues involved in the studies of arsenic-rich Tl mineralizations is acknowledged with pleasure. We acknowledge Czech-NanoLab Research Infrastructure supported by MEYS CR (LM2018110) for the financial support of the measurements. The interpretation of the Raman spectrum was performed in accordance with the state task, state registration No. ААAА-А19-119092390076-7.

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Received: 2021-02-02
Accepted: 2021-05-27
Published Online: 2022-05-27
Published in Print: 2022-05-27

© 2022 Mineralogical Society of America

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  21. Erratum
https://doi.org/10.2138/am-2022-8003
Keywords for this article
Gungerite; new mineral species; Tl-As-Sb sulfosalt; Raman spectroscopy; crystal structure; covalent bonds; Vorontsovskoe gold deposit

Articles in the same Issue

  1. Periodic and non-periodic stacking in molybdenite (MoS2) revealed by STEM
  2. The effect of halogens (F, Cl) on the near-liquidus crystallinity of a hydrous trachyte melt
  3. Occurrence of tuite and ahrensite in Zagami and their significance for shock-histories recorded in martian meteorites
  4. Zolenskyite, FeCr2S4, a new sulfide mineral from the Indarch meteorite
  5. Refined estimation of Li in mica by a machine learning method
  6. Olivine in picrites from continental flood basalt provinces classified using machine learning
  7. The glass transition and the non-Arrhenian viscosity of carbonate melts
  8. Etching of fission tracks in monazite: Further evidence from optical and focused ion beam scanning electron microscopy
  9. The low-temperature shift of antigorite dehydration in the presence of sodium chloride: In situ diffraction study up to 3 GPa and 700 °C
  10. Chemistry-dependent Raman spectral features of glauconite and nontronite: Implications for mineral identification and provenance analysis
  11. Experimental determination of solubility constants of saponite at elevated temperatures in high ionic strength solutions
  12. Hydrothermal troctolite alteration at 300 and 400 °C: Insights from flexible Au-reaction cell batch experimental investigations
  13. Timescales and rates of intrusive and metamorphic processes determined from zircon and garnet in migmatitic granulite, Fiordland, New Zealand
  14. In situ chemical and isotopic analyses and element mapping of multiple-generation pyrite: Evidence of episodic gold mobilization and deposition for the Qiucun epithermal gold deposit in Southeast China
  15. Hydrothermal mineralization of celadonite: Hybridized fluid–basalt interaction in Janggi, Korea
  16. Gungerite, TlAs5Sb4S13, a new thallium sulfosalt with a complex structure containing covalent As-As bonds
  17. Nitscheite, (NH4)2[(UO2)2(SO4)3(H2O)2]·3H2O, a new mineral with an unusual uranyl-sulfate sheet
  18. Protocaseyite, a new decavanadate mineral containing a [Al4(OH)6(H2O)12]6+ linear tetramer, a novel isopolycation
  19. Fission-track etching in apatite: A model and some implications
  20. Hydrothermal monazite trumps rutile: Applying U-Pb geochronology to evaluate complex mineralization ages of the Katbasu Au-Cu deposit, Western Tianshan, Northwest China
  21. Erratum
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