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The minerals of carletonite group, fluorcarletonite, KNa4Ca4[Si8O18](CO3)4(F,OH)·H2O and carletonite, Na4Ca4[Si8O18](CO3)4(OH,F)·H2O, were investigated using a multi-method approach. A detailed comparative chemical study of the minerals was carried out using electron probe microanalysis and Fourier transform infrared spectroscopy. Using X-ray techniques and the results obtained, geometrical and distortion characteristics of the mineral structures are calculated and the successful crystal-structure refinement of these two natural compounds are given. Using spectroscopic and luminescence methods and ab initio calculations, it is shown that hole defects (CO3)•– are responsible for the colouration of the samples studied. Luminescence due to 5d–4f transition in Ce3+ ions is observed in both investigated compounds. Moreover, luminescence attributed to intrinsic luminescence, corresponding to the decay of electronic excitations of (CO3)2– complexes in the carletonite sample, is registered for the first time in phyllosilicates. An analysis of the optical absorption spectra and g-tensor values suggests that (CO3)•– defects in the crystal structure are localised in the C1 positions. Identification of these specific properties for these sheet silicates, with a two-dimensional infinite tetrahedral polymerisation, indicates that carletonites could be prospective materials for novel phosphors and luminophores.

The results of combined single-crystal X-ray diffraction, electron probe microanalysis, Fourier microspectroscopy, and photoluminescence spectroscopy study of crystals of turkestanite from the Dara-i-Pioz deposit, Tien-Shan Mountains, Tajikistan are reported. It is a single-layer sheet silicate belonging to the ekanite group with a steacyite structural type. Averaged major-element analysis provided (wt.%): K2O 4.13(6), CaO 8.1(1), Na2O 2.3(1), ThO2 25.8(4), UO2 3.6(4) and SiO2 55.9(1). The averaged crystal-chemical formula for the studied turkestanite is (Th0.84U0.12)Σ0.96(Ca1.24Na0.65)Σ1.89(K0.75☐0.25)Σ1.00Si8O19.72(OH)0.28. Single-crystal structural refinement of turkestanite gave tetragonal, space group P4/mcc, a = 7.5708(3) Å, c = 14.7300(11) Å, V = 844.27(6) Å3 and Z = 2. Luminescence of the uranyl ion (UO2)2+ is observed in turkestanite. In the excitation spectrum, the bands corresponding to a charge transfer transition from the 2p states of the ligand to the 5f state of uranium were found.

Sulfhydrylbystrite, Na5K2Ca(Al6Si6O24)(S5)(SH), cell parameters a = 12.9567(6) Å, c = 10.7711(5) Å, space group P31c, is a new mineral belonging to the cancrinite group. It was found at Malaya Bystraya lazurite deposit, Lake Baikal area, Eastern Siberian Region, Russia, associated with lazurite, calcite, diopside, phlogopite and pyrite. The mineral develops at the margins of masses of lazurite, replacing it in some areas with the formation of nonequilibrium lazurite-diopside-sulfhydrylbystrite association. It is translucent, yellow to orange, with vitreous lustre, yellow streak and Mohs hardness of 4.5–5. The empirical formula, based on 12 (Si + Al), is Na5.17K1.87Ca0.99[Al6.01Si5.99O24](S5)0.862–(SH0.86)Cl0.07, Z = 2. The crystal structure of sulfhydrylbystrite may be described as an ABAC stacking of six-membered rings of SiO4 and AlO4 tetrahedra and extra-framework cations and anions located within structural cages. There are two type of cages, cancrinite and losod, stacked into chains at (0, 0, z) and (⅔, ⅓, z), respectively. The cancrinite cage hosts Ca2+ and (SH)– ions, whereas the (S5)2– polyanion is in the losod cage associated with Na+ and K+ cations. In addition, (SH)– and (S5)2– anions are detected in the structure of a mineral for the first time.For comparison, a structural and compositional study of a bystrite sample from the same deposit was carried out. Bystrite is confirmed to contain pentasulfide anions in the losod cages, similar to those of sulfhydrylbystrite, in contrast to previous studies. However, bystrite has chloride in cancrinite cages, whereas sulfhydrylbystrite has hydrosulfide in that position. The unit-cell parameters are distinctly different: bystrite has a = 12.8527(6) Å, c = 10.6907(5) Å in the same P31c space group.

The structures of tokkoite, K2Ca4[Si7O18OH](OH,F) and tinaksite, K2Ca2NaTi[Si7O18OH]O from the Murun massif (Russia) were refined from single-crystal X-ray diffraction data in the triclinic space groupP1̄. Average crystallographic data area≈ 10.423,b≈ 12.477,c≈ 7.112 Å, α ≈ 89.92°, β ≈ 99.68°, γ ≈ 92.97°,V≈ 910.5 Å3for tokkoite;a≈ 10.373,b≈ 12.176,c≈ 7.057 Å, α ≈ 90.82°, β ≈ 99.22°, γ ≈ 92.80°,V≈ 878.5 Å3for tinaksite. The substantial similarities between the geometrical parameters of the tokkoite and tinaksite structures led us to conclude that the two minerals are isostructural. However, major differences of tokkoite with respect to tinaksite are larger lattice constants, especially concerning thebparameter, longer distances, especially ; larger values of the M1–M3 and O20–O2 bond lengths, and a stronger distortion of the M1 polyhedron. Mössbauer analysis showed that significant trivalent iron is present,VIFe3+40.0(7)% in tokkoite and 12.8(3)% in tinaksite. It is confirmed that 2Ca(M1+M2)2++ (F,OH)(O20)–↔ Ti(M1)4++ Na(M2)++ O(O20)–is the exchange reaction that describes the relation between tokkoite and tinaksite. In addition, this exchange reaction causes local stress involving mainly the M1 site and its interaction with the M2 and M3 sites.

A crystal chemical study of narsarsukite from the Murun alkaline massif, Russia has been carried out combining single-crystal X-ray diffraction, electron microprobe analyses, micro-Fourier transform infrared (FTIR) spectroscopy and X-ray photoelectron spectroscopy (XPS). The narsarsukite single crystals are tetragonal (space group I4/m) with unit-cell parameters: 10.7140(1) ≤ a ≤ 10.7183(2) Å and 7.9478(1) ≤ c ≤ 7.9511(1) Å. The XPS analysis showed that Fe occurs in the mineral as Fe3+, whereas the FTIR spectrum showed that the sample studied is anhydrous. The average crystal chemical formula of the Murun narsarsukite is: Na2.04K0.01(V0.015+Ti0.74Zr0.01Al0.01Fe0.223+Mg0.01)1.00Si4.00(O10.74F0.23OH0.03)11.00. Structural disorder at octahedral and interstitial sites was modelled and also discussed in consideration of the main substitutional mechanism Ti4+ + O2– ↔ Fe3+ + (F–, OH–) active in the structure of the mineral.