Crystal Chemistry, Isomorphism, and Thermal Conversions of Extra-Framework Components in Sodalite-Group Minerals

Abstract

Isomorphic substitutions of extra-framework components in sodalite-group aluminosilicate minerals and their thermal conversions have been investigated using infrared, Raman, electron spin resonance (ESR), as well as ultraviolet, visible and near infrared (UV–Vis–near IR) absorption spectroscopy methods and involving chemical and X-ray diffraction data. Sodalite-related minerals from gem lazurite deposits (haüyne, lazurite, and slyudyankaite) are characterized by wide variations in S-bearing extra-framework components including SO42− and various polysulfide groups (S2●−, S3●−, S4●− radical anions, and S4 and S6 neutral molecules) as well as the presence of CO2 molecules. Heating at 700 °C under reducing conditions results in the transformation of initial S-bearing groups SO42− and S3●− to a mixture of S2−, HS−, S2●−, and S4●− and transformation of CO2 to a mixture of CO32− and C2O42− or HC2O4− anionic groups. Further heating at 800 °C in air results in the decomposition of carbonate and oxalate groups, restoration of the SO42− and S3●− groups, and a sharp transformation of the framework. The HS− anion is stable only under reducing conditions, whereas the S3●− radical anion is the most stable polysulfide group. The HS−-dominant sodalite-group mineral sapozhnikovite forms a wide solid-solution series with sodalite. The conditions required for the formation of HS−- and CO20-bearing sodalite-group minerals are discussed.