A. E. Zadov

Crystal structure of larnite β-Ca2SiO4 and specific features of polymorphic transitions in dicalcium orthosilicate

The crystal structure of larnite, a natural analog of synthetic β-Ca2SiO4, has been determined: a = 5.5051(3) Å, b = 6.7551(3) Å, c = 9.3108(5) Å, β = 94.513(4)o, sp. gr. P21/n, Z = 4, and R1 = 0.0532 for 1071 reflections with I > 2σ (I). Larnite was found in skarn xenoliths (Lakargi, Kabardino-Balkaria, Russia). The mineral structure is based on a heteropolyhedral glaserite-like framework of interconnected Ca polyhedra and isolated [SiO4] tetrahedra. Based on an analysis of the layer-by-layer packing of atoms in the structures of larnite and other Ca2SiO4 polymorphs, the structural features and mechanisms of transitions from high-temperature (α, α′L, and α′H) to low-temperature (β and γ) Ca2SiO4 modifications, as well as their relationship with natural glaserite-like orthosilicates (merwinite Ca3Mg[SiO4]2 and bredigite Ca7Mg[SiO4]4), have been considered. The most likely atomic arrangement in hypothetical Ca2SiO4 models has been calculated by the method of atomistic potentials.

Shirokshinite, K(NaMg2)Si4O10F2, a new mica with octahedral Na from Khibiny massif, Kola Peninsula: descriptive data and structural disorder

Shirokshinite, K(NaMg 2 )Si 4 O 10 F 2 , is the analogue of tainiolite, K(LiMg 2 )Si 4 O 10 F 2 , with the M 1 octahedron fully occupied by Na instead of Li. It was found in the Kirovskii underground apatite mine (Kukisvumchorr Mountain, Khibiny massif, Kola Peninsula, Russia) as a late hydrothermal mineral in a small hyperalkaline pegmatite embedded in ristschorrite. Shirokshinite is associated with microcline, kupletskite, aegirine, natrolite, lorenzenite, calcite, remondite-(Ce), donnayite-(Y), mckelveyite-(Y) and galena. Crystals are usually skeletal and coarse hexagonal [001] prismatic. Shirokshinite is transparent to translucent, colourless to pale greyish, hardness Mohs9 ∼2.5; D(calc) = 2.922 g/cm 3 . Optically biaxial (-), α = 1.526(1), β = 1.553(2), γ = 1.553(2); 2V meas = −5(5)°, 2V calc = −0°; Y = b , Z ∼ a , Xc = 3(2)°. The IR spectrum of shirokshinite is unique even if close to that of tainiolite: in particular, the presence of Na + instead of Li + shifts some bands towards low-frequencies. Single-crystal diffraction data (Mo K α-radiation) gave a = 5.269(2), b = 9.092(9), c = 10.198(3) A, β = 100.12(7)°, Z = 2, 1 M -polytype, space group C 2/ m. Structure anisotropic refinement converged R = 0.13 for 715 observed reflections. Evidence of stacking faults in the structure is discussed and compared with the so called Ďurovic effect. The very little ditrigonal distortion in spite of the large dimension of the Na octahedron is discussed in comparison with tainiolite. A critical revision of old published data indicating octahedral Na in micas shows that this hypothesis was biased by the low quality of the chemical analyses.

Fukalite: An example of an OD structure with two-dimensional disorder

Abstract The real crystal structure of fukalite, Ca4Si2O6(OH)2(CO3), was solved by means of the application of order-disorder (OD) theory and was refined through synchrotron radiation diffraction data from a single crystal. The examined sample came from the Gumeshevsk skarn copper porphyry deposit in the Central Urals, Russia. The selected crystal displays diffraction patterns characterized by strong reflections, which pointed to an orthorhombic sub-structure (the “family structure” in the OD terminology), and additional weaker reflections that correspond to a monoclinic real structure. The refined cell parameters are a = 7.573(3), b = 23.364(5), c = 11.544(4) Å, β = 109.15(1)°, space group P21/c. This unit cell corresponds to one of the six possible maximum degree of order (MDO) polytypes, as obtained by applying the OD procedure. The derivation of the six MDO polytypes is presented in the Appendix1. The intensity data were collected at the Elettra synchrotron facility (Trieste, Italy); the structure refinement converged to R = 0.0342 for 1848 reflections with I > 2σ(I) and 0.0352 for all 1958 data. The structure of fukalite may be described as formed by distinct structural modules: a calcium polyhedral framework, formed by tobermorite-type polyhedral layers alternating along b with tilleyitetype zigzag polyhedral layers; silicate chains with repeat every fifth tetrahedron, running along a and linked to the calcium polyhedral layers on opposite sides; and finally rows of CO3 groups parallel to (100) and stacked along a.

Calcio-olivine γ-Ca2SiO4: I. Rietveld refinement of the crystal structure

AbstractThe structure of the natural mineral calcio-olivine (γ-Ca2SiO4) found in skarn xenoliths in the region of the Lakargi Mountain (North Caucasus, Kabardino-Balkaria, Russia) is refined by the Rietveld method [a = 5.07389(7) Å, b = 11.21128(14) Å, c = 6.75340(9) Å, V = 384.170(5) Å3, Z = 4, ρcalcd = 2.98 g/cm3, space group Pbnm]. The X-ray diffraction pattern of a powdered sample is recorded on a STOE STADI MP diffractometer [λCuKα1; Ge(111) primary monochromator; 6.00° < 2θ < 100.88°; step width, 2.5° in 2θ; number of reflections, 224]. All calculations are performed with the WYRIET (version 3.3) software package. The structural model is refined in the anisotropic approximation to Rp = 6.44, Rwp = 8.52, Rexp = 5.85, RB = 4.98, RF = 6.90, and s = 1.46. It is shown that the sample under investigation is a mixture of several mineral phases, among which calcio-olivine (the natural analogue of the γ-Ca2SiO4 compound) (83%), hillebrandite (13%), and wadalite (4%) are dominant. Only the scale factors and the unit cell parameters are refined for hillebrandite Ca2SiO3(OH)2 [a = 3.63472(16) Å, b = 16.4140(10) Å, c = 11.7914(8) Å, space group Cmc21, Z = 6] and wadalite Ca6Al5Si2O16Cl3 (a = 12.0088 Å, space group, I

Kyanoxalite, a new cancrinite-group mineral species with extraframework oxalate anion from the Lovozero alkaline pluton, Kola peninsula

\bar 4

The sulfite anion in ettringite-group minerals: a new mineral species hielscherite, Ca3Si(OH)6(SO4)(SO3)·11H2O, and the thaumasite–hielscherite solid-solution series

3dZ = 4). The results of the structure refinement of the main component of the sample confirm that the mineral calcio-olivine is isostructural to the synthetic compound γ-Ca2SiO4. The structure of this compound is formed by the heteropolyhedral framework composed of Ca octahedra joined together into olivine-like ribbons and isolated Si tetrahedra.

Calcioolivine, γ-Ca2SiO4, an old and New Mineral species

Abstract Megawite is a perovskite-group mineral with an ideal formula CaSnO3 that was discovered in altered silicate-carbonate xenoliths in the Upper Chegem caldera, Kabardino-Balkaria, Northern Caucasus, Russia. Megawite occurs in ignimbrite, where it forms by contact metamorphism at a temperature >800ºC and low pressure. The name megawite honours the British crystallographer Helen Dick Megaw (1907-2002) who did pioneering research on perovskite-group minerals. Megawite is associated with spurrite, reinhardbraunsite, rondorfite, wadalite, srebrodolskite, lakargiite, perovskite, kerimasite, elbrusite-(Zr), periclase, hydroxylellestadite, hydrogrossular, ettringite-group minerals, afwillite, hydrocalumite and brucite. Megawite forms pale yellow or colourless crystals up to 15 μm on edge with pseudo-cubic and pseudo-cuboctahedral habits. The calculated density and average refractive index are 5.06 g cm-3 and 1.89, respectively. Megawite is Zr-rich and usually crystallizes on lakargiite, CaZrO3. The main bands in the Raman spectrum of megawite are at: 159, 183, 262, 283, 355, 443, 474, 557 and 705 cm-1. The unit-cell parameters and space group of megawite, derived from electron back scattered diffraction, are: a = 5.555(3), b = 5.708(2), c = 7.939(5) Å, V = 251.8(1) Å3, Pbnm, Z = 4; they are based on an orthorhombic structural model for the synthetic perovskite CaSn0.6Zr0.4O3.

Refined structure of afwillite from the northern Baikal region

Kyanoxalite, a new member of the cancrinite group, has been identified in hydrothermally altered hyperalkaline rocks and pegmatites of the Lovozero alkaline pluton, Kola Peninsula, Russia. It was found at Mount Karnasurt (holotype) in association with nepheline, aegirine, sodalite, nosean, albite, lomonosovite, murmanite, fluorapatite, loparite, and natrolite and at Mt. Alluaiv. Kyanoxalite is transparent, ranging in color from bright light blue, greenish light blue and grayish light blue to colorless. The new mineral is brittle, with a perfect cleavage parallel to (100). Mohs hardness is 5–5.5. The measured and calculated densitiesare 2.30(1) and 2.327 g/cm3, respectively. Kyanoxalite is uniaxial, negative, ω = 1.794(1), ɛ = 1.491(1). It is pleochroic from colorless along E to light blue along O. The IR spectrum indicates the presence of oxalate anions C2O42− and water molecules in the absence of CO32− Oxalate ions are confirmed by anion chromatography. The chemical composition (electron microprobe; water was determined by a modified Penfield method and carbon was determined by selective sorption from annealing products) is as follows, wt %: 19.70 Na2O, 1.92 K2O, 0.17 CaO, 27.41 Al2O3, 38.68 SiO2, 0.64 P2O5, 1.05 SO3, 3.23 C2O3, 8.42 H2O; the total is 101.18. The empirical formula (Z = 1) is (Na6.45K0.41Ca0.03)Σ6.89(Si6.53Al5.46O24)[(C2O4)0.455(SO4)0.13(PO4)0.09(OH)0.01]Σ0.68 · 4.74H2O. The idealized formula is Na7(Al5−6Si6−7O24)(C2O4)0.5−1 · 5H2O. Kyanoxalite is hexagonal, the space group is P63, a = 12.744(8), c = 5.213(6) -ray powder diffraction pattern are as follows, [d, [A] (I, %)(hkl)]: 6.39(44) (110), 4.73 (92) (101), 3.679 (72) (300), 3.264 (100) (211, 121), 2.760 (29) (400), 2.618 (36) (002), 2.216, (29) (302, 330). According to the X-ray single crystal study (R = 0.033), two independent C2O4 groups statistically occupy the sites on the axis 63. The new mineral is the first natural silicate with an additional organic anion and is the most hydrated member of the cancrinite group. Its name reflects the color (κɛανgoΣς is light blue in Greek) and the species-forming role of oxalate anions. The holotype is deposited at the Fersman Mineralogical Museum of the Russian Academy of Sciences, Moscow, registration no. 3735/1.