Synthesis and thermal stability of 2 \frac{1}{2}-octahedral sodium mica,NaMg2.5 (OH)2∫i4O10]

A new 2 \(\frac{1}{2}\) -octahedral sheet silicate, NaMg_2.5 Si₄O₁₀ (OH)₂, has been synthesized from oxide mixtures in the temperature range 500–600°C at pressures between 1 and 5 kb. The lattice parameters are a ₀ = 5.298 Å, b ₀ = 9.047 Å, c ₀ = 9.479 Å and ß=99.55°. X-ray data are given in the text. At temperatures above 605° C/1 kb and 630° C/5 kb, it decomposes to magnesiorichterite plus quartz.     

Natural and synthetic ferroglaucophane

Amphiboles approximating the composition of the ferroglaucophane end member, Na₂Fe₃Al₂Si₈O₂₂(OH)₂, have not been found in nature prior to 1969. Chemical, physical and petrologic data of four specimens of that mineral are given, two from Southern Italy and two from New Caledonia (Black, 1970). The ferroglaucophane end member was synthesized in seeded runs at 500° C, 5000 bars fluid pressure with oxygen fugacity defined by the wüstite-magnetite (WM) buffer. X-ray data and cell dimensions (a=9.686 Å, b=17.89, c=5.317, β=103° 45.2′ V=894.9 ų) are presented along with microprobe data that confirm the end member composition. Under these conditions of synthesis the ferroglaucophane grew metastably, however. Stability relations of the synthetic end member and of one natural specimen were investigated in a temperature range from 250° C to 500° C and at 3 and 5 kb with different oxygen buffers. At relatively low oxygen fugacities (WM buffer, QFM buffer) ferroglaucophane breaks down above 350–360° C. Under more oxidizing conditions (HM buffer) ferroglaucophane may not be stable even at very low temperatures. Mineral facies and chemical bulk composition of rocks that would favor the natural occurrence of ferroglaucophane are discussed. As assemblages with ferroglaucophane can have crystallized only below a very specific upper temperature limit, it is proposed to direct some attention towards that mineral.     

On dehydroxylation mechanisms of a biotite in vacuo and in oxygen

The dehydroxylation mechanisms of a biotite in the temperature range 300–800° C at controlled oxygen pressures were studied by infrared (IR) and Mössbauer spectroscopies. At low pressure, the lack of O₂ delays the oxidation of Fe⁺² and simultaneous loss of hydrogen but favours the loss of OH associated with octahedral vacancies in comparison with heat treatment in air. Stoichiometrical considerations based on the facts that the octahedral cations are randomly distributed and all Fe⁺² is oxidized lead to the conclusion that all the OH groups initially coordinated to Fe⁺² must be lost during the oxidation process.     

Raman scattering and lattice vibrations of Ni2SiO4 spinel at elevated temperature

Raman spectra of Ni₂SiO₄ spinel (O _h ⁷ Z=8) have been measured in the temperature range from 20 to 600 °C and the Raman active vibrations (A _1g +E _g +3F _2g ) have been assigned. A calculation of the optically active lattice vibrations of this spinel has been made, assuming a potential function which combines general valence and short range force constants. The values of the force constants at 20 and 500 °C have been calculated from the vibrational frequencies of the observed Raman spectra and infrared (IR) spectral data. The Ni spinel at 20 °C has a prominently small Si-O bond stretching force constant of K(SiO)=2.356 ～ 2.680 md/Å and a large Ni-O bond stretching constant of K(NiO)=0.843 ～ 1.062 md/Å and these force constants at 500 °C decrease to K(SiO)=2.327 ～ 2.494 md/Å and K(NiO)=0.861 ～ 0.990 md/Å. The Si-O bond is noticeably weakened at high temperatures, despite the small thermal expantion from 1.657 Å (20 °C) to 1.660 Å (500 °C). These changes of the interatomic force constants of the spinel at high temperatures are in accord with the thermal structure changes observed by X-ray diffraction study. The weakened Si-O bond is consistent with the fact that Si atoms in the spinel lattice can diffuse at significant rates at elevated temperature.     

Five-coordinate Cd in the crystal structure of triploidite-type Cd2(AsO4)(OH)

This paper reports on hydrothermal synthesis and crystal structure refinement of dicadmium arsenate hydroxide, Cd₂(AsO₄)(OH), obtained at 220 °C and autogenous pressure. Its crystal structure is monoclinic, space group P2₁/a, with a = 13.097(3), b = 14.089(3), c = 10.566(2) Å, β = 108.38(3)°, V = 1850.2(6) ų (Z = 16). It is isotypic with the members of the triploidite group of minerals and synthetic compounds, and thus shows a close topological relationship with the triplite group. The complex framework contains edge- and corner-sharing CdO₄(OH) and CdO₄(OH)₂ polyhedra, linked via corner-sharing to AsO₄ tetrahedra (average As—O distances range between 1.682 and 1.688 Å). Four five-coordinated Cd sites are at the centers of distorted trigonal bipyramids (average Cd—O distances are between 2.225 and 2.251 Å), whereas the remaining four Cd sites have a distorted octahedral coordination environment (average Cd—O distances are between 2.297 and 2.320 Å). The positions of all the hydrogen atoms were located in a difference-Fourier map and refined with an isotropic displacement parameter. The hydrogen-bonds are weak to very weak. The unusual five-coordination of Cd is briefly discussed in relation to comparable minerals and compounds. Among triploidite-type compounds, Cd₂(AsO₄)(OH) is the member with the largest unit cell reported so far, and the second known arsenate member.     

Crystal chemistry, thermal expansion, and Raman spectra of hydroxyl-clinohumite: implications for water in Earth’s interior

Two samples of hydroxyl-clinohumite, sample SZ0407B with approximate composition Mg_8.674(14)Fe_0.374(4)(Si_0.99(1)O₄)₄(OH)₂ and sample SZ0411B with composition Mg₉(SiO₄)₄(OH)₂, were synthesized at 12 GPa and 1,250 °C coexisting with olivine. Unit-cell parameters determined by single-crystal X-ray diffraction are given as follows: a = 4.7525(4) Å, b = 10.2935(12) Å, c = 13.7077(10) Å, α = 100.645(9)°, V = 659.04(9) Å³ for SZ0407B, and a = 4.7518(6) Å, b = 10.2861(12) Å, c = 13.7008(9) Å, α = 100.638(9)°, V = 658.15(9) Å³ for SZ0411B. Single-crystal X-ray intensity data were collected for crystal structure refinements of both samples. Relative to the pure-Mg sample, Fe decreases M3–OH bond lengths by ~0.010(3) Å, consistent with some ferric iron ordering into M3. Raman spectroscopy shows two strong bands in the lattice-mode region at 650 and 690 cm^?1 in the Fe-bearing sample, which are not observed in the pure-Mg sample. Spectra in the H₂O region show at least five bands, which are deconvolved into seven distinct O–H-stretching modes. Thermal expansion measurements were carried out for both samples from 153 to 787 K by single-crystal X-ray diffraction. The average a-, b-, c-axial and volumetric thermal expansion coefficients (10^?6 K^?1) are 10.5(1), 12.3(2), 12.5(2) and 34.9(5) for SZ0407B, respectively, and 11.1(1), 12.6(3), 13.7(3), 36.8(6) for SZ0411B, respectively. After heating, the unit-cell parameters were refined again for each sample at ambient condition, and no significant changes were observed, indicating no significant oxidation or dehydration during the experiment. For the DHMS phases along the brucite–forsterite join, linear regression gives a systematic linear decrease in expansivity with increasing density. Further, substitution of ferrous iron into these structures decreases thermal expansivity, making the Fe-bearing varieties slightly stiffer.     

Arcanite from Fumarole Exhalations of the Tolbachik Volcano (Kamchatka,Russia) and Its Crystal Structure

The crystal structure (R = 0.0194) of arcanite β-K₂SO₄ was studied on a single crystal from exhalations of the Arsenatnaya fumarole, Tolbachik Volcano (Kamchatka, Russia). The mineral crystallizes at a temperature of ≥350–430°C and associates with langbeinite, aphthitalite, hematite, tenorite, johillerite, and others. Arcanite is orthorhombic, Pnma, a = 7.4763(2) Å, b = 5.77262(16) Å, c = 10.0630(3) Å, V = 434.30(2) ų, Z = 4. Its structure contains isolated SO₄ tetrahedra, whereas K cations center ten- and nine-fold polyhedra.     

Non-convergent ordering and displacive phase transition in pigeonite: in situ HT XRD study

A natural Ca-rich pigeonite (En₄₇Fs₄₃Wo₁₀), free of augite exsolution products, was studied by in situ high-temperature single-crystal X-ray diffraction. The sample, monoclinic P2 ₁ /c (a=9.719(7) Å, b=8.947(9) Å, c=5.251(3) Å, β=108.49(5), V=433.0(6) ų), was annealed up to 1000 °C to induce a phase transition from P2 ₁ /c to C2/c symmetry. Complete single-crystal X-ray diffraction data collections were carried out in situ at 650, 750, 850 and 950 °C after the crystal had reached equilibrium for the Fe–Mg intracrystalline exchange reaction at each temperature. The variation, with increasing temperature, of lattice parameters, of intensity of hkl reflections with h + k=2n + 1 (which vanish at high temperature) and of some geometrical parameters from structure refinement, showed that the displacive phase transition P2 ₁ /c?C2/c was continuous in character. This contrasts with the first-order character for the HT phase transition in pigeonite containing significantly less calcium.     

“Pseudosinhalite”, a new hydrous MgAl-borate: synthesis, phase characterization, crystal structure, and PT-stability

The new synthetic phase Mg₂Al₃O[BO₄]₂(OH) provisionally named “pseudosinhalite” is optically, chemically, and structurally similar to the mineral sinhalite, MgAl[BO₄], isostructural with forsterite. It grows hydrothermally from appropriate bulk compositions in the range 4–40?kbar at temperatures that increase with pressure (～650?→?900?°C), and it breaks down at higher temperatures to sinhalite?+?corundum?+?H₂O. At P?≥?20?kbar single-phase products of euhedral twinned crystals could often be obtained. Pseudosinhalite is monoclinic with a?=?7.455 (1) Å, b?=?4.330 (1) Å, c?=?9.825 (2) Å, β?=?110.68 (1)°, and space group P2₁/c. Crystal structure analysis reveals that pseudosinhalite is also based on hexagonal close packing (hcp) of oxygen atoms with Mg and Al in octahedral and B in tetrahedral coordination. In pseudosinhalite the winged octahedral chains in the plane of hcp are not straight as in sinhalite but have a zigzag, 3-repeat period (Dreierkette), and only 1/10 instead of 1/8 of all tetrahedral sites are filled by boron. Hydrogen is located at a split position between two oxygen atoms O5—O5, which are only 2.550 Å apart and thus generate strong hydrogen bonding. This may be responsible for the absence of an hydroxyl absorption band between 2800?cm^?1 and 3500?cm^?1 in the powder IR spectrum. The equilibrium breakdown curve of pseudosinhalite to form sinhalite, corundum, and water was determined by bracketing experiments to pass through 10?kbar, 745?°C and 35?kbar, 950?°C, giving a slope of about 8?°C/kbar, similar to dehydration curves of some silicates at high pressure. In nature pseudosinhalite could have been misidentified as sinhalite. A possible appearance, like sinhalite in boron-rich skarns, would require more aluminous bulk compositions than for sinhalite at relatively low temperatures. However, pseudosinhalite might also form as a hydrous alteration product of sinhalite at low temperatures, perhaps in association with szaibelyite, MgBO₂(OH).     

The crystal and magnetic structure of Li-aegirine LiFe3+Si2O6: a temperature-dependent study

Single crystals of Li-aegirine LiFe³⁺Si₂O₆ were synthesized at 1573?K and 3?GPa, and a polycrystalline sample suitable for neutron diffraction was produced by ceramic sintering at 1223?K. LiFe³⁺Si₂O₆ is monoclinic, space group C2/c, a=9.6641(2)?Å, b= 8.6612(3)?Å, c=5.2924(2)?Å, β=110.12(1)^° at 300?K as refined from powder neutron data. At 229?K Li-aegirine undergoes a phase transition from C2/c to P2₁ /c. This is indicated by strong discontinuities in the temperature variation of the lattice parameters, especially for the monoclinic angle β and by the appearance of Bragg reflections (hkl) with h+k≠2n. In the low-temperature form two non-equivalent Si-sites with 〈SiA–O〉=1.622?Å and 〈SiB–O〉=1.624?Å at 100?K are present. The bridging angles of the SiO₄ tetrahedra O3–O3–O3 are 192.55(8)° and 160.02(9)° at 100?K in the two independent tetrahedral chains in space group P2₁ /c, whereas it is 180.83(9)° at 300?K in the high-temperature C2/c phase, i.e. the chains are nearly fully expanded. Upon the phase transition the Li-coordination changes from six to five. At 100?K four Li–O bond lengths lie within 2.072(4)–2.172(3)?Å, the fifth Li–O bond length is 2.356(4)?Å, whereas the Li–O3?A bond lengths amount to 2.796(4)?Å. From ⁵⁷Fe Mössbauer spectroscopic measurements between 80 and 500?K the structural phase transition is characterized by a small discontinuity of the quadrupole splitting. Temperature-dependent neutron powder diffraction experiments show first occurrence of magnetic reflections at 16.5?K in good agreement with the point of inflection in the temperature-dependent magnetization of LiFe³⁺Si₂O₆. Distinct preordering phenomena can be observed up to 35?K. At the magnetic phase transition the unit cell parameters exhibit a pronounced magneto-striction of the lattice. Below T _N Li-aegirine shows a collinear antiferromagnetic structure. From our neutron powder diffraction experiments we extract a collinear antiferromagnetic spin arrangement within the a–c plane.     

Crystal structure of xinganite

Xinganite is a new REE-Be-rich silicate discovered in China. Its ideal formula is: (Y, Ce)Be SiO₄ OH. The mineral is of monoclinic system. The intensity data were collected with a single-crystal four-circle diffractometer. The lattice parameters are: a=4.7681 (± 0.00263) Å,b=7.7657 (± 0.00686) Å, c=9.9301 (± 0.00639) Å; α =90°, β=90.171° (±0.0053°), γ=90° space group p2¹/c;,Z=4. The crystal structure has been determined by direct methods and electron density synthesis methods. The least squares refinement gave a final discrepancy indexR=0.086. The crystal structural analysis shows that xinganite is of datolite-type structure.     

The thermal expansion of anhydrite to 1000° C

The thermal expansion of anhydrite, CaSO₄, has been measured from 22° to 1,000° C by X-ray diffraction, using the Guinier-Lenné heating powder camera. The heating patterns were calibrated with Guinier-Hägg patterns at 25° C, using quartz as internal standard. Heating experiments were run on natural anhydrite (Bancroft, Ontario), which at room temperature has lattice constants in close agreement with those of synthetic material. The orthorhombic unit cell at 22° C (space group Amma) has a=7.003 (1) Å, b=6.996 (2) Å and c=6.242 (1) Å, V=305.9 (2) ų. At room temperature, the thermal expansion coefficients α and β (α in °C^?1×10⁴, β in °C^?2×10⁸) are for a, 0.10, ?0.69; for b, 0.08, 0.19; for c, 0.18, 1.60; for V, 0.37, 1.14. Second-order coefficients provide an excellent fit over the whole range to 1,000° C.     

Crystal chemical characteristics of α-CaSi2O5, a new high pressure calcium silicate with five-coordinated silicon synthesized at 1500°C and 10 GPa

The crystal structure of α-CaSi₂O₅ synthesized at conditions of 1500°C and 10 GPa, has been solved and refined in centrosymmetric space group P , using single crystal X-ray diffraction data. The composition (Z=4) and unit cell are Ca_1.02Si_1.99O₅ by EPMA analysis and a=7.243(2) Å, b=7.546(4) Å, c=6.501(4) Å, α=81.43(5)°, β=84.82(4)°, γ=69.60(3)°, V=329.5(3) ų, yielding the density value, 3.55 g/cm³. The structure is closely related to that of titanite, CaTiSiO₅ and features the square-pyramid five-fold coordination of silicon by oxygen. The ionic radius for five-coordinated Si calculated from the bond distances is 0.33 Å. The substantial deviation of valence sum for Ca indicates the existence of local strain and the instability of α-CaSi₂O₅ at room pressure.     

Xitieshanite—A new ferric sulphate mineral

Xitieshanite is a new ferric sulfate mineral discovered in the oxidation zone of a Pb-Zn deposit at Xitieshan, Qinghai Province, China. The typical crystal of xitieshanite is a rhombic rectangle. It is bright green in colour with a light yellow tint. Luster vitrous Translucent to almost transparent. Streak yellow. Cleavage imperfect. Fracture uneven or conchoidal. H. (Vickers)=62.6kg/mm². Specific gravity=1.99_obs(2.02_calc,) Pleochroism strong, and axial colours: X=colourless to pale yellow, Y=pale yellow, Z=light yellow with greenish tint. It is optically positive, biaxial, 2V=77°,r v. Refractive indices:N _x =1.536,N _y =1.570,N _z =1.628. Extinction parallel and inclined. Elongation positive and negative. X-ray single-crystal study shows it is monoclinic. Space groupP2₁/a. Unit cell parameters:a=14.102,b=6.908,c=10.673 Å, β=111.266°,V=968.9, ų,Z=4. The powder pattern of xitieshanite gave the strongest lines: 6.67(6)(201), 6.09(5)(110), 5.69(5)(011), 4.96(10)(002), 4.81(10)(211), 4.21(5)(112), and 3.90(9)(211). Chemical analysis gave Al₂O₃ 0.01, Fe₂O₃ 26.15, FeO 0.18, MgO 0.03, CaO 0.09, K₂O 0.03, Na₂O 0.07, SO₃ 27.69, H₂O 45.02, total 99.27%, corresponding to the chemical formula: Fe²⁺ (SO₄)(OH) · 7H₂O. The DTA curve shows respectively three strong endothermic peaks at 85°, 170°, and 735°C, and a weak peak at 460°C. The TGA curve shows a loss of weight in three different steps. The infrared spectral curve of xitieshanite demonstrates that it has two principal absorption bands at 3,350 and 1,225–1,003 cm^?1 and two subordinate bands at 1,620 and 603 cm^?1.     

Kobyashevite, Cu5(SO4)2(OH)6·4H2O, a new devilline-group mineral from the Vishnevye Mountains, South Urals, Russia

A new mineral kobyashevite, Cu₅(SO₄)₂(OH)₆·4H₂O (IMA 2011–066), was found at the Kapital’naya mine, Vishnevye Mountains, South Urals, Russia. It is a supergene mineral that occurs in cavities of a calcite-quartz vein with pyrite and chalcopyrite. Kobyashevite forms elongated crystals up to 0.2 mm typically curved or split and combined into thin crusts up to 1?×?2 mm. Kobyashevite is bluish-green to turquoise-coloured. Lustre is vitreous. Mohs hardness is 2½. Cleavage is {010} distinct. D(calc.) is 3.16 g/cm³. Kobyashevite is optically biaxial (?), α 1.602(4), β 1.666(5), γ 1.679(5), 2 V(meas.) 50(10)°. The chemical composition (wt%, electron-microprobe data) is: CuO 57.72, ZnO 0.09, FeO 0.28, SO₃ 23.52, H₂O(calc.) 18.39, total 100.00. The empirical formula, calculated based on 18 O, is: Cu_4.96Fe_0.03Zn_0.01S_2.01O_8.04(OH)_5.96·4H₂O. Kobyashevite is triclinic, $ P\overline{\,1 } $ , a 6.0731(6), b 11.0597(13), c 5.5094(6)?Å, α 102.883(9)°, β 92.348(8)°, γ 92.597(9)°, V 359.87(7)?ų, Z?=?1. Strong reflections of the X-ray powder pattern [d,Å-I(hkl)] are: 10.84–100(010); 5.399–40(020); 5.178–12(110); 3.590–16(030); 2.691–16(20–1, 040, 002), 2.653–12(04–1, 02–2), 2.583–12(2–11, 201, 2–1–1), 2.425–12(03–2, 211, 131). The crystal structure (single-crystal X-ray data, R?=?0.0399) сontains [Cu₄(SO₄)₂(OH)₆] corrugated layers linked via isolated [CuO₂(H₂O)₄] octahedra; the structural formula is CuCu₄(SO₄)₂(OH)₆·4H₂O. Kobyashevite is a devilline-group member. It is named in memory of the Russian mineralogist Yuriy Stepanovich Kobyashev (1935–2009), a specialist on mineralogy of the Urals.     

Ivsite,Na<Subscript>3</Subscript>H(SO<Subscript>4</Subscript>)<Subscript>2</Subscript>, a new mineral from volcanic exhalations of fumaroles of the Fissure Tolbachik Eruption of the 50th Anniversary of the Institute of Volcanology and Seismology,Far East Branch,Russian Academy of Sciences

Fine-granular (<0.1 mm) flattened colorless transparent crystals of ivsite form white aggregates. The empirical formula (Na_2.793Cu_0.056)_2.849HS_2.016O₈ is close to the ideal Na₃H(SO₄)₂. The structure was refined up to R = 0.040. Ivsite has a monoclinic symmetry, P2₁/c, a = 8.655(1) Å, b = 9.652(1) Å, c = 9.147(1) Å, β = 108.76(1)°, V = 723.61(1) ų, Z = 4. Na atoms occur at six- and seven-fold sites (NaO₆ and NaO₇); S atoms, in isolated SO₄ tetrahedrons; these polyhedrons form a three-dimensional framework. The diagnostic lines of powder diffraction patterns (d[Å]–I–hkl) are 4.010–53–12-1, 3.949–87–012, 3.768–100–210, 3.610–21–20-2, 3.022–22–031, 2.891–42–22-2, 2.764–49–31-1, and 2.732–70–13-1.     

Alkali in phlogopite and amphibole and their effects on phase relations in metasomatized peridotites: a high-pressure study

Subsolidus phase relations for a K-doped lherzolite are investigated in the model system K₂O–Na₂O–CaO–FeO–MgO–Al₂O₃–SiO₂–H₂O at 1.5–6.0 GPa and 680–1,000°C. Phlogopite is ubiquitous and coexists with Ca-amphibole up to 3.2 GPa and 900°C. High-pressure phlogopites show a peculiar mineral chemistry dependent on pressure: e.g., at 5.5 GPa and 680°C, excess of Si (up to 3.4 apfu) coupled with deficiency in Al (as low as 0.58 apfu) and K + Na (as low as 0.97 apfu), suggest a significant amount of a talc/10 Å phase component ([v]^XIISi₁K_?1Al _?1 ^IV , where [v]^XII is interlayer vacancy). Mixed layering or solid solution relations between high-pressure phlogopites and the 10 Å phase, Mg₃Si₄O₁₀(OH)₂ nH₂O, are envisaged. Phlogopite modal abundance, derived by weighted least squares, is maximum at high-pressure and relative low-temperature conditions and therefore along the slab–mantle interface (10.3 ± 0.7 wt.%, at 4.8 GPa, 680°C). In phlogopite-bearing systems, Ca-amphibole breaks down between 2.5 and 3.0 GPa, and 1,000°C, through the water conservative reaction 5(pa + 0.2 KNa_?1) + 17en + 15phl = (10di + 4jd) + 5py + 12fo + 20(phl + 0.2 talc), governed by bulk composition and pressure-dependent variations of K/OH in K-bearing phases and as a result, it does not necessarily imply a release of fluid.     

Crystal structures of iron bearing tetrahedrite and tennantite at 25 and 250°C by means of Rietveld refinement of synchrotron data

Rietveld refinement of X-ray synchrotron data was performed for two synthetic tetrahedrite samples, with 0.61 and 1.83 Fe atoms, and two synthetic tennantite samples with 0.10 and 1.23 Fe atoms p.f.u. M₁₂(Sb,As)₄S₁₃. Measurements were performed at 25 and 250°C. For both the phases, increased Fe substitution is reflected in the increased tetrahedral ‘Cu1’–S distance (‘Cu1’ is a site of Fe substitution) and Cu2–S distances. Cu2 was refined as a split position; the Cu2–Cu2 split about the plane of the S1₂S2 triangle is about 0.56 and 0.65 Å for tetrahedrite and tennantite, respectively. Cu2–Cu2 distances in the structure cavity are 2.8–2.9 Å. Between 25 and 250°C, the lattice parameter a increased by 0.02–0.04 Å and the interatomic distances by 0.01 Å on an average. Thermal expansion coefficients of little-substituted samples are similar to those of unsubstituted samples, whereas thermal expansion appears to decrease with increasing substitution by Fe. The Cu2–Cu2 split increases at 250°C by about 0.1 Å for tetrahedrite and by more than 0.15 Å for tennantite but the cage expansion is minimal so that the Cu2–Cu2 distances in the cavity decrease with temperature. Difference Fourier maps indicate that there is little residual electron density left between the two Cu2 half-sites in tetrahedrite but this inter-site density is substantially higher in tennantite. It increases with temperature, especially in the little-substituted tennantite sample.     

Investigations of MX-1 tridymite by 29Si MAS NMR — Modulated structures and structural phase transitions

MX-1 tridymite is one of the room-temperature polymorphs of SiO₂ tridymite and has an underlying monoclinic structure (Cc) with incommensurate modulations along a ^* and c ^* (Hoffmann et al. 1983; Löns and Hoffmann 1987). With increasing temperature up to 500° C, MX-1 is reported to experience at least five structural phase transitions. However, its structures and the relationships to other tridymite polymorphs are unclear. We present here a ²⁹Si MAS NMR study of the room-temperature incommensurate structure of MX-1 and its structural phase transitions up to 540° C. Our results suggest that at room temperature, all the Si sites in MX-1 tridymite are in positions with similiar ∠Si-O-Si of ～150° and are consistent with the presence of two incommensurate modulations proposed by Hoffmann et al. (1983). Simulations of the spectra yield modulation amplitudes of 1.33 and 0.87 ppm, corresponding to 0.009 and 0.006 Å for Si-Si. The maximum atomic displacements along a and b due to the modulations appear to be ～0.01–0.02 Å. The structural phase transitions of MX-1 are significantly different from those of MC tridymite below 220° C. Our high temperature results confirm that MX-1 tridymite transforms to the H5 phase at about 65° C. The most important transition occurs near 110° C, where the H5 phase transforms to a phase yielding a single, narrow NMR peak, indicating the disappearance of the superstructure and possibly the onset of the dynamic averaging. The NMR lineshapes of H5 are consistent with the metrically orthorhombic unit cell and commensurate superstructure of 2a, 2b and 10c proposed by Graetsch and Flörke (1991). The phase present above 110° C is probably similar to the OC phase, but has a mean ∠Si-O-Si of ～152.0° at 113° C, 152.9° at 185° C and 154.1° at 500° C. The transitions at ～160 and 220° C for MX-1 are subtle and probably due to impurity MC. Analysis of the modulations in the OS phase of MC tridymite indicates that their amplitudes are of the order of 0.02 Å, significantly less than the value 0.3 Å proposed by Nukui et al. (1979).     

Avdoninite: New data,crystal structure and refined formula K<Subscript>2</Subscript>Cu<Subscript>5</Subscript>Cl<Subscript>8</Subscript>(OH)<Subscript>4</Subscript> · 2H<Subscript>2</Subscript>O

The paper reports new findings of avdoninite from deposits of active fumaroles in the Second Scoria Cone at the Northern Breach of the Great Fissure Tolbachik Eruption, Tolbachik Volcano, Kamchatka Peninsula, Russia. The crystal structure of the mineral has been determined for the first time, which has allowed reliable determination of its space group and unit cell dimensions, refinement of its formula K₂Cu₅-Cl₈(OH)₄ · 2H₂O, and correct indexing of its X-ray powder diffraction pattern. Avdoninite is monoclinic, space group P2₁/c, a = 11.592(2), b = 6.5509(11), c = 11.745(2) Å, β = 91.104(6)°, V = 891.8(3) ų, Z = 2. The crystal structure of this mineral has been determined on a single crystal R ₁ [F > 4σ (F)] = 0.063. It is based on sheets of copper–oxo-chloride complexes [Cu₅Cl₈(OH)₄]^2– parallel to (100). The K⁺ cation and H₂O molecules are interlayers.