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A structure hierarchy for silicate minerals: sheet silicates
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- Frank C. Hawthorne, Yulia A. Uvarova, Elena Sokolova
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- Journal:
- Mineralogical Magazine / Volume 83 / Issue 1 / February 2019
- Published online by Cambridge University Press:
- 09 November 2018, pp. 3-55
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The structure hierarchy hypothesis states that structures may be ordered hierarchically according to the polymerisation of coordination polyhedra of higher bond-valence. A hierarchical structural classification is developed for sheet-silicate minerals based on the connectedness of the two-dimensional polymerisations of (TO4) tetrahedra, where T = Si4+ plus As5+, Al3+, Fe3+, B3+, Be2+, Zn2+ and Mg2+. Two-dimensional nets and oikodoméic operations are used to generate the silicate (sensu lato) structural units of single-layer, double-layer and higher-layer sheet-silicate minerals, and the interstitial complexes (cation identity, coordination number and ligancy, and the types and amounts of interstitial (H2O) groups) are recorded. Key aspects of the silicate structural unit include: (1) the type of plane net on which the sheet (or parent sheet) is based; (2) the u (up) and d (down) directions of the constituent tetrahedra relative to the plane of the sheet; (3) the planar or folded nature of the sheet; (4) the layer multiplicity of the sheet (single, double or higher); and (5) the details of the oikodoméic operations for multiple-layer sheets. Simple 3-connected plane nets (such as 63, 4.82 and 4.6.12) have the stoichiometry (T2O5)n (Si:O = 1:2.5) and are the basis of most of the common rock-forming sheet-silicate minerals as well as many less-common species. Oikodoméic operations, e.g. insertion of 2- or 4-connected vertices into 3-connected plane nets, formation of double-layer sheet-structures by (topological) reflection or rotation operations, affect the connectedness of the resulting sheets and lead to both positive and negative deviations from Si:O = 1:2.5 stoichiometry. Following description of the structural units in all sheet-silicate minerals, the minerals are arranged into decreasing Si:O ratio from 3.0 to 2.0, an arrangement that reflects their increasing structural connectivity. Considering the silicate component of minerals, the range of composition of the sheet silicates completely overlaps the compositional ranges of framework silicates and most of the chain-ribbon-tube silicates.
Rinkite-(Y), Na2Ca4YTi(Si2O7)2OF3, a seidozerite-supergroup TS-block mineral from the Darai-Pioz alkaline massif, Tien-Shan mountains, Tajikistan: Description and crystal structure
- Leonid A. Pautov, Atali A. Agakhanov, Vladimir Yu. Karpenko, Yulia A. Uvarova, Elena Sokolova, Frank C. Hawthorne
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- Journal:
- Mineralogical Magazine / Volume 83 / Issue 3 / June 2019
- Published online by Cambridge University Press:
- 29 June 2018, pp. 373-380
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Rinkite-(Y), ideally Na2Ca4YTi(Si2O7)2OF3, is a new rinkite-group (seidozerite-supergroup) TS-block mineral from the Darai-Pioz alkaline massif, Tian-Shan mountains, Tajikistan. The mineral is of hydrothermal origin. It occurs as aggregates (up to 1.5 cm long) of acicular crystals 0.1–1.0 mm thick, and as separate elongated columnar, flattened-prismatic crystals up to 1 cm long with rectangular or rhombic sections up to 0.5 mm across. Associated minerals are quartz, aegirine, microcline, neptunite, pectolite, calcite, eudialyte-group minerals, fluorite, titanite, turkestanite, kupletskite, galena, albite and pyrochlore-group minerals. Crystals are transparent and colourless to occasionally white, with a vitreous lustre. Rinkite-(Y) has a white streak, uneven, conchoidal fracture and does not fluoresce under a cathode or ultraviolet light. Cleavage is very good on {100}, no parting was observed, Mohs hardness is ~5, and it is brittle, Dmeas. = 3.44(2) g/cm3, Dcalc. = 3.475 g/cm3. It is biaxial (+) with refractive indices (λ = 590 nm) α = 1.662(2), β = 1.666(2), γ = 1.685(5); 2Vmeas. = 50(3) and 2Vcalc. = 49.7°. It is nonpleochroic. Rinkite-(Y) is monoclinic, space group P21/c, a = 7.3934(5), b = 5.6347(4), c = 18.713(1) Å, β = 101.415(2)° and V = 764.2(2) Å3. The six strongest reflections in the X-ray powder diffraction data [d(Å), I, (hkl)] are: 3.057, 100, (006, $\bar{2}$12, 210); 2.688, 28, (016); 9.18, 24, (002); 2.929, 17, ($\bar{2}$13, 211); 3.559, 15, (104, 014) and 2.783, 14, (021). The empirical formula calculated on 18 (O + F) is Na2.11(Ca3.74Sr0.03Mn0.03)Σ3.80(Y0.50Nd0.16Ce0.16Gd0.07Dy0.06Sm0.05Pr0.03La0.03${\rm U}_{0.01}^{{\rm 4 + }} {\rm )}_{\Sigma 1.07}{\rm (T}{\rm i}_{0.85}{\rm N}{\rm b}_{0.17}{\rm W}^{6+}_{0.01}{\rm T}{\rm a}_{0.01}{\rm )}_{\Sigma 1.04}\left( {{\rm S}{\rm i}_{4.03}{\rm O}_{14}} \right){\rm O}_{1.40}{\rm F}_{2.60}$ with Z = 2. The ideal formula is Na2Ca4YTi(Si2O7)2OF3. The crystal structure was refined on a twinned crystal to R1 = 4.59% on the basis of 1489 unique reflections (F > 4σF) and is a framework of TS (Titanium-Silicate) blocks. The TS block consists of HOH sheets (H – heteropolyhedral, O – octahedral) parallel to (100). In the O sheet, the Ti-dominant [6]MO1 site ideally gives 1 Ti apfu. The [8]MO2 and [6]MO3 sites are ideally occupied by Na and (NaCa) apfu. In the H sheet, the [7]MH site is occupied by Ca1.13Y0.50REE0.37, (REE = rare-earth element), ideally (CaY), <MH–φ> = 2.415 Å and the [7]AP site is occupied by Ca1.81REE0.19, ideally Ca2, <AP–φ> = 2.458 Å. The MH + AP sites ideally give (Ca3Y) apfu. The MH and AP polyhedra and Si2O7 groups constitute the H sheet. Linkage of H and O sheets via common vertices of MH and AP polyhedra and Si2O7 groups with MO1–3 polyhedra results in a TS block. The TS block in rinkite-(Y) exhibits linkage 1 and stereochemistry typical for the rinkite group (Ti = 1 apfu) of the seidozerite supergroup. For rinkite-(Y), the ideal structural formula of the form AP2MH2MO4(Si2O7)2$ \left( {{\rm X}_{\rm M}^{\rm O} } \right)_2\left( {{\rm X}_{\rm A}^{\rm O} } \right)_2{\rm is }\;\left( {{\rm C}{\rm a}_3{\rm Y}} \right){\rm Na}\left( {{\rm NaCa}} \right){\rm Ti}\left( {{\rm S}{\rm i}_2{\rm O}_7} \right)_2\left( {{\rm OF}} \right){\rm F}_2 $ with Z = 2. The mineral is named rinkite-(Y) as it is structurally identical to rinkite-(Ce) and Y is the dominant rare-earth element.