Five samples of differently colored sodalite-group minerals from gem lazurite deposits were studied by means of electron microprobe and wet chemical analyses, infrared, Raman, electron spin resonance (ESR) and UV-Visible spectroscopy, and X-ray diffraction. Various extra-framework components (SO₄²⁻, S²⁻ and Cl⁻ anions, S₃^•−, S₂^•− and SO₃^•− radical anions, H₂O, CO₂, COS, cis- as well as trans- or gauche-S₄ neutral molecules have been identified. It is shown that S₃^•− and S₄ are the main blue and purple chromophores, respectively, whereas the S₂^•− yellow chromophore and SO₃^•− blue chromophore play a subordinate role. X-ray diffraction patterns of all samples of sodalite-group minerals from lazurite deposits studied in this work contain superstructure reflections which indicate different kinds of incommensurate modulation of the structures.

Nine samples of carbonate-free sodalite-group minerals, including those with abnormally high contents of polysulfide groups, fluoride anion and carbon dioxide molecules as well as synthetic fluoraluminate sodalite-type compound Na₈(Si₇Al₅O₂₄)(AlF₆)^3–·5H₂O, have been studied by means of electron microprobe analyses, infrared and Raman spectroscopy; the CO₂ content was determined using the selective sorption of gaseous ignition products. This article describes a semi-quantitative method for estimating the content of carbon dioxide molecules in these minerals, based on IR spectroscopy data. The data obtained demonstrate the existence of a sulfide sodalite-group mineral with the idealized formula Na₇(Si₆Al₆O₂₄)(S₃⁻)·H₂O, which differs significantly from the formula Na₆Ca₂(Si₆Al₆O₂₄)S^2–₂ accepted for lazurite. According to single-crystal X-ray structural analysis, in the F-rich sodalite-group mineral from the Eifel paleovolcanic region, Germany with the idealized formula Na₇(Si₆Al₆O₂₄)F⁻·nH₂O fluorine occurs as an isolated F⁻ anion, unlike synthetic F-rich sodalite-type compounds.

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.

The isomorphism of S-bearing feldspathoids belonging to the cancrinite, sodalite, tugtupite, vladimirivanovite, bystrite, marinellite and scapolite structure types has been investigated using a multimethodical approach based on infrared, Raman and 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. Sapozhnikovite Na₈(Al₆Si₆O₂₄)(HS)₂ and sulfite and thiosulfate analogues of cancrinite are synthesized hydrothermally and characterized by means of electron microprobe analyses, powder X-ray diffraction and Raman spectroscopy. The possibility of the incorporation of significant amounts of SO₄²⁻, S₄ and SO₃²⁻ in the crystal structures of cancrisilite, sulfhydrylbystrite and marinellite, respectively, has been established for the first time. Thermal conversions of S-bearing groups in the synthetic sulfite cancrinite and sapozhnikovite analogues as well as natural vladinirivanovite and S₄-bearing haüyne under oxidizing and reducing conditions have been studied using the multimethodical approach. The SO₄²⁻ and S²⁻ anions and the S₃^•– radical anion are the most stable S-bearing species under high-temperature conditions (in the range of 700–800 °C); their ratio in the heated samples is determined by the redox conditions and charge-balance requirement. The HS⁻ and S₅²⁻ anions are stable only under highly reducing conditions.

The new mineral nöggerathite-(Ce) was discovered in a sanidinite volcanic ejectum from the Laach Lake (Laacher See) paleovolcano in the Eifel region, Rhineland-Palatinate, Germany. Associated minerals are sanidine, dark mica, magnetite, baddeleyite, nosean, and a chevkinite-group mineral. Nöggerathite-(Ce) has a color that ranges from brown to deep brownish red, with adamantine luster; the streak is brownish red. It occurs in cavities of sanidinite and forms long prismatic crystals measuring up to 0.02 × 0.03 × 1.0 mm, with twins and random intergrowths. Its density calculated using the empirical formula is 5.332 g/cm³. The Vickers hardness number (VHN) is 615 kgf/mm², which corresponds to a Mohs’ hardness of 5½. The mean refractive index calculated using the Gladstone–Dale equation is 2.267. The Raman spectrum shows the absence of hydrogen-bearing groups. The chemical composition (electron microprobe holotype/cotype in wt %) is as follows: CaO 5.45/5.29, MnO 4.19/4.16, FeO 7.63/6.62, Al₂O₃ 0.27/0.59, Y₂O₃ 0.00/0.90, La₂O₃ 3.17/3.64, Ce₂O₃ 11.48/11.22, Pr₂O₃ 1.04/0.92, Nd₂O₃ 2.18/2.46, ThO₂ 2.32/1.98, TiO₂ 17.78/18.69, ZrO₂ 27.01/27.69, Nb₂O₅ 17.04/15.77, total 99.59/99.82, respectively. The empirical formulae based on 14 O atoms per formula unit (apfu) are: (Ce_0.59La_0.165Nd_0.11Pr_0.05)_Σ0.915Ca_0.82Th_0.07Mn_0.50Fe_0.90Al_0.045Zr_1.86Ti_1.88Nb_1.07O₁₄ (holotype), and (Ce_0.57La_0.19Nd_0.12Pr_0.05Y_0.06)_Σ0.99Ca_0.79Th_0.06Mn_0.49Fe_0.77Al_0.10Zr_1.89Ti_1.96Nb_1.00O₁₄ (cotype). The simplified formula is (Ce,Ca)₂Zr₂(Nb,Ti)(Ti,Nb)₂Fe²⁺O₁₄. Nöggerathite-(Ce) is orthorhombic, of the space group Cmca. The unit cell parameters are: a = 7.2985(3), b = 14.1454(4), c = 10.1607(4) Å, and V = 1048.99(7) ų. The crystal structure was solved using single-crystal X-ray diffraction data. Nöggerathite-(Ce) is an analogue of zirconolite-3O, ideally CaZrTi₂O₇, with Nb dominant over Ti in one of two octahedral sites and REE dominant over Ca in the eight-fold coordinated site. The strongest lines of the powder X-ray diffraction pattern (d, Å (I, %) (hkl)) are: 2.963 (91) (202), 2.903 (100) (042), 2.540 (39) (004), 1.823 (15) (400), 1.796 (51) (244), 1.543 (20) (442), and 1.519 (16) (282), respectively. The type material is deposited in the collections of the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, Russia (registration number 5123/1).

Lazurite and other lazurite-related minerals (LRMs) containing sulfur in both sulfate and sulfide forms are sodalite-type compounds with various extraframework species, of which the tendency to order leads to structural modulations with a period that is either commensurate or incommensurate with the period of the basic lattice. In this work, the structures of incommensurately modulated monoclinic LRMs are re-examined based on the superstructure of slyudyankaite, formerly known as triclinic lazurite. Similarities and differences between three one-dimensionally modulated LRMs and cubic LRM structures modulated in several directions are discussed. Assumptions are made on how the symmetry of the structure and the composition of the crystal can affect the period of structural modulation.