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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
From the journal American Mineralogist

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 Na6.97Ca0.88K0.10Σ7.96Al5.96Si6.04Σ12O24SO41.092S30.55S0.052Cl0.040.72H2O.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.

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

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