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On the crystal chemistry of sulfur-rich lazurite, ideally Na7Ca(Al6Si6O24)(SO4)(S3)–·nH2O

  • Anatoly N. Sapozhnikov , Vladimir L. Tauson , Sergey V. Lipko , Roman Yu. Shendrik , Valery I. Levitskii , Lyudmila F. Suvorova , Nikita V. Chukanov and Marina F. Vigasina
Published/Copyright: January 29, 2021
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American Mineralogist
From the journal American Mineralogist Volume 106 Issue 2

Abstract

Dark blue lazurite from the Malo-Bystrinskoe lazurite deposit, Baikal Lake area, Eastern Siberian region, Russia, was analyzed by electron microprobe and revealed an unusually high content of total sulfur corresponding to 8.3 wt% S. The relative content of sulfur in sulfate and sulfur in sulfide form was determined by wet chemical analysis. The H2O content was measured by means of differential thermal analysis in combination with mass spectrometry and infrared (IR) spectroscopy. The charge-balanced empirical formula of lazurite calculated on the basis of 12 (Al+Si) atoms per formula unit was N a 6.97 C a 0.88   K 0.10 Σ 7.96 A l 5.96 S i 6.04 Σ 12 O 24 S O 4 1.09 2 − S 3 − 0.55   S 0.05 2 − C l 0.04 ⋅ 0.72 H 2 O . The presence of H2O molecules and (S3)– and (SO4)2– groups was confirmed by the combination of IR, Raman, electron paramagnetic resonance (EPR), and X‑ray photoelectron spectroscopy (XPS) methods. The idealized formula of lazurite is Na7Ca[Al6Si6O24](SO4)2–(S3)–·H2O, and it is believed that extra-framework cations and anions are grouped into clusters of [Na3Ca·SO4]3+ and [Na4(S3)–]3+. The types of isomorphous substitutions in nosean and haüyne are discussed. Lazurite is a clathrate-type mineral, which may be an effective (S3)– sensor due to the stability of the trisulfur radical anion in isolated cages of the crystal structure. This specific feature makes it possible to study the behavior of this ubiquitous radical anion over larger T and P ranges as compared to free species. This kind of lazurite, with oxidized and reduced sulfur species, seems to be appropriate for the estimation of the fugacity of SO2 and O2 in metasomatic systems forming lazurite-containing rocks. The systematic presence of incommensurate modulations is a unique structural feature of Baikal lazurite and may be an important marker indicating provenance of the mineral.

Keywords: Microporous mineral structure; lazurite; sulfide radical ion; X‑ray diffraction; spectroscopy; superstructure

Acknowledgments and Funding

The authors thank anonymous reviewers and A.G. Bulakh for constructive criticism and useful comments. The research was performed within the framework of state task IX.124.3, registration no. AAAA-A17-117041910035-2. The IR spectroscopy study was partly performed in accordance with state task, registration no. AAAA-A19-119092390076-7. The Raman spectroscopy study was supported by the Russian Foundation for Basic Research, grant no. 18-29-12007. The study of dehydration of samples was carried out with the support of the grant no. RSF 18-72-10085.

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Received: 2019-10-09
Accepted: 2020-06-10
Published Online: 2021-01-29
Published in Print: 2021-02-23

© 2021 Walter de Gruyter GmbH, Berlin/Boston

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https://doi.org/10.2138/am-2020-7317
Keywords for this article
Microporous mineral structure; lazurite; sulfide radical ion; X‑ray diffraction; spectroscopy; superstructure

Articles in the same Issue

  1. Effect of water on carbonate-silicate liquid immiscibility in the system KAlSi3O8- CaMgSi2O6-NaAlSi2O6-CaMg(CO3)2 at 6 GPa: Implications for diamond-forming melts
  2. Jasonsmithite, a new phosphate mineral with a complex microporous framework, from the Foote mine, North Carolina, U.S.A
  3. Titanium in calcium amphibole: Behavior and thermometry
  4. Phase relationships in the system ZnS-CuInS2: Insights from a nanoscale study of indium-bearing sphalerite
  5. Major and trace element composition of olivine from magnesian skarns and silicate marbles
  6. Decompression experiments for sulfur-bearing hydrous rhyolite magma: Redox evolution during magma decompression
  7. On the crystal chemistry of sulfur-rich lazurite, ideally Na7Ca(Al6Si6O24)(SO4)(S3)–·nH2O
  8. Experimental evaluation of a new H2O-independent thermometer based on olivine-melt Ni partitioning at crustal pressure
  9. Contrasting compositions between phenocrystic and xenocrystic olivines in the Cenozoic basalts from central Mongolia: Constraints on source lithology and regional uplift
  10. The composition of garnet in granite and pegmatite from the Gangdese orogen in southeastern Tibet: Constraints on pegmatite petrogenesis
  11. Formation of metasomatic tourmalinites in reduced schists during the Black Hills Orogeny, South Dakota
  12. New insights into the crystal chemistry of sauconite (Zn-smectite) from the Skorpion zinc deposit (Namibia) via a multi-methodological approach
  13. The new mineral crowningshieldite: A high-temperature NiS polymorph found in a type IIa diamond from the Letseng mine, Lesotho
  14. Elucidating the natural–synthetic mismatch of Pb2+Te4+O3: The redefinition of fairbankite to P b 12 2 + T e 4 + O 3 11 S O 4
  15. Are the thermodynamic properties of natural and synthetic Mg2SiO4-Fe2SiO4 olivines the same?
  16. American Mineralogist thanks the 2020 reviewers
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