On the temperature conditions of formation of pink S4-containing haüyne from the Malo-Bystrinsky lazurite deposit (East Siberia, Russia)

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Abstract

Thermal transformations of ornamental pink haüyne from the Malo-Bystrinskoye lazurite deposit in the Baikal region containing S4 molecules as a chromophore were studied using electron microprobe analysis, synchronous thermal analysis, high-temperature X-ray diffraction and Raman scattering methods. A scheme of transformations of the S4 molecule with the formation of a blue chromophore, the S3•– radical anion, was proposed. The upper temperature limit of the existence of sodalite group minerals with S4 molecules (about 400 °C) was established.

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About the authors

A. N. Sapozhnikov

Vinogradov Institute of Geochemistry Siberian Branch RAS

Email: slipko@yandex.ru
Russian Federation, Irkutsk

V. L. Tauson

Vinogradov Institute of Geochemistry Siberian Branch RAS

Email: slipko@yandex.ru
Russian Federation, Irkutsk

S. V. Lipko

Vinogradov Institute of Geochemistry Siberian Branch RAS

Author for correspondence.
Email: slipko@yandex.ru
Russian Federation, Irkutsk

B. S. Danilov

Institute of Earth’s Crust Siberian Branch RAS

Email: slipko@yandex.ru
Russian Federation, Irkutsk

N. V. Chukanov

Federal Research Center of Problems of Chemical Physics and Medicinal Chemistry RAS

Email: slipko@yandex.ru
Russian Federation, Chernogolovka, Moscow Oblast

References

  1. Bacci M., Cucci C., Del Federico E., Ienco A., Jerschow A., Newmand J. M., Picollo M. An integrated spectroscopic approach for the identification of what distinguishes Afghan lapis lazuli from others. Vibrat. Spectr. 2009. Vol. 49. P. 80—83.
  2. Bolotina N. B., Chukanov N. V., Sapozhnikov A. N., Zubkova N. V., Pekov I. V., Varlamov D. A., Vigasina M. F., Bulakh M. O., Yapaskurt V. O., Ksenofontov D. A. Vladimirivanovite revised: General crystal chemistry and isomorphous substitutions of extra-framework species. Minerals. 2024. Vol. 14. Paper 883. https://doi.org/10.3390/min14090883
  3. Chukanov N. V., Sapozhnikov A. N., Shendrik R. Yu., Vigasina M. F., Steudel R. Spectroscopic and crystal-chemical features of sodalite-group minerals from gem lazurite deposits. Minerals. 2020a. Vol. 10. Paper 1042. https://doi.org/10.3390/min10111042
  4. Chukanov N. V., Vigasina M. F., Zubkova N. V., Pekov I. V., Schäfer C., Kasatkin A. V., Yapaskurt V. O. New aspects of the application of infrared and Raman spectroscopy to the characterization of extraframework components in sodalite-group minerals. Minerals. 2020b. Vol. 10. Paper 363.
  5. https://doi.org/10.3390/min10040363
  6. Chukanov N. V., Shendrik R. Yu., Vigasina M. F., Pekov I. V., Sapozhnikov A. N., Shcherbakov V. D., Varlamov D. A. Crystal chemistry, isomorphism, and thermal conversions of extra-framework components in sodalite-group minerals. Minerals. 2022a. Vol. 12. Paper 887. https://doi.org/10.3390/min12070887
  7. Chukanov N. V., Shchipalkina N. V., Shendrik R. Yu., Vigasina M. F., Tauson V. L., Lipko S. V., Varlamov D. A., Shcherbakov V. D., Sapozhnikov A. N., Kasatkin A. V., Zubkova N. V., Pekov I. V. Isomorphism and mutual transformations of S-bearing components in feldspathoids with microporous structures. Minerals. 2022b. Vol. 12. Paper 1456. https://doi.org/10.3390/min12111456
  8. Ivanov V. G., Sapozhnikov A. N. Lazurites of the USSR. Novosibirsk: Nauka, 1985. 173 p. (in Russian).
  9. Fedyaeva M., Lepeshkin S., Chukanov N. V., Oganov A. R. Mutual transformations of polysulfide chromophore species in sodalite-group minerals: A DFT study on S6 decomposition. ChemPhysChem. 2024. Vol. 25. N 20. e202400532. https://doi.org/10.1002/cphc.202400532
  10. Felsche J., Luger S., Baerlocher Ch. Crystal structures of the hydro-sodalite Na6[AlSiO4]6•8H2O and of the anhydrous sodalite Na6{AlSiO4]6. Zeolites. 1986. Vol. 6. P. 367—372.
  11. Ledé B., Demortier A., Gobeltz-Hautecœur H., Lelieur J.-P., Picquenard E., Duhayo C. Observation of the ν3 Raman band of S3– inserted into sodalite cages. J. Raman Spectr. 2007. Vol. 38. P. 1461—1468.
  12. Lo Giudice A., Angelici D., Re A., Gariani G., Borghi A., Calusi S. et al. Protocol for lapis lazuli provenance determination: evidence for an Afghan origin of the stones used for ancient carved artefacts kept at the Egyptian Museum of Florence (Italy). Archeol. Anthropol. Sci. 2017. Vol. 9. P. 637—651. https://doi.org/10.1007/s12520-016-0430-0
  13. Ostroumov E., Fritsch E., Faulques E., Chauvet O. Etude spectrometrique de la lazurite du Pamir. Tajikistan. Canad. Miner. 2002. Vol. 40. P. 885—893. https://doi.org/10.2113/gscanmin.40.3.885 (in French).
  14. Rejmak P. Computational refinement of the puzzling red tetrasulfur chromophore in ultramarine pigments. Phys. Chem. Chem. Phys. 2020. Vol. 39. P. 22684—22698. https://doi.org/10.1039/DOCP03019H
  15. Ruivo A. C., Coutino-Gonzalez E., Santos M., Baekelant W., Fron E., Roeffaers M. B.J., Pina F., Hofkens J., Laia C. A. T. Highly photoluminescent sulfide clusters confined in zeolites. J. Phys. Chem. C. 2018. Vol. 122. P. 14761—14770. https://doi.org/10.1021/acs.jpcc.8b01247
  16. Sapozhnikov A. N., Ivanov V. G., Levitskii V. I., Piskunova L. F. Structural-mineralogical features of lazurites of South-Western Pamir. Zapiski VMO (Proc. Russian Miner. Soc.). 1993. Vol. 122. P. 36—45 (in Russian).
  17. Sapozhnikov A. N., Tauson V. L., Lipko S. V., Shendrik R. Yu., Levitskii V. I., Suvorova L. F., Chukanov N. V., Vigasina M. F. On the crystal chemistry of sulfur-rich lazurite, ideally Na7Ca(Al6Si6O24)(SO4)(S3)–•nH2O. Amer. Miner. 2021. Vol. 106. P. 226—234.
  18. Sapozhnikov A. N., Chukanov N. V., Shendrik R. Yu., Vigasina M. F., Tauson V. L., Lipko S. V., Belakovskiy D. I., Levitskii V. I., Suvorova L. F., Ivanova L. A. Lazurite: Validation as a mineral species with the formula Na7Ca(Al6Si6O24)(SO4) S3•–•H2O and new data. Zapiski RMO (Proc. Russian Miner. Soc.). 2021. Vol. 150. N4. P. 92—102. (in Russian, English translation: Geol. Ore Deposits. 2022. Vol. 64. N 7. P. 470—475. https://doi.org/10.1134/S1075701522070078)
  19. Sapozhnikov A. N., Bolotina N. B., Chukanov N. V., Shendrik R. Yu., Kaneva E. V., Vigasina M. F., Ivanova L. A., Tauson V. L., Lipko S. V. Slyudyankaite, Na28Ca4(Si24Al24O96)(SO4)6(S6)1/3(CO2)•2H2O, a new sodalite-group mineral from the Malo-Bystrinskoe lazurite deposit, Baikal Lake area. Amer. Miner. 2023. Vol. 108. P. 1805—1817. https://doi.org/10.2138/am-2022—8598
  20. Vorob’ev E. I., Matonin V. N. New data on geology and genesis of lazurite deposits in Baikal region. In: Ferrous-magnesium metasomatism and ore formation. Moscow: Nauka, 1980. P. 140—157 (in Russian).

Supplementary files

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2. Fig. 1. Grains of initial pinkish-lilac S4-bearing haüyne with white patches of calcite (upper level) and these annealed in the air at 400 °C (lower level).

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3. Fig. 2. Raman spectra of initial pinkish-lilac haüyne (a) and this annealed in the air at 400 °C (б).

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4. Fig. 3. Curves of weight loss (TG), thermal effects (DSC) and mass spectra of gases released under thermolysis.

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5. Fig. 4. Temperature dependence of the unit cell edge under sample recording in “heating-cooling” regime.

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