Characteristics of moderate- to large-scale landslides triggered by the <Emphasis Type="Italic">M</Emphasis><Subscript><Emphasis Type="Italic">w</Emphasis></Subscript> 7.8 2015 Gorkha earthquake and its aftershocks

The M _w 7.8 2015 Gorkha earthquake and its aftershocks significantly impacted the lives and economy of Nepal. The consequences of landslides included fatalities, property losses, blockades of river flow, and damage to infrastructural systems. Co-seismic landslides triggered by this earthquake were significantly widespread and pose a major geodisaster. There were tens of thousands of landslides triggered by the earthquake, majority of which were distributed in between the epicenter of the main shock and the M _w 7.3 aftershock. Although 14,670 landslides triggered by this earthquake were identified, only approximately 23% of them were of moderate to large scale with areas greater than 100 m². Of the moderate- to large-scale landslides identified, just over 90% were triggered by the main shock and smaller aftershocks prior to the major (M _w 7.3) aftershock, while nearly 10% were triggered by the ground shaking induced by the major aftershock. Moreover, the number of landslides triggered by the 2015 Gorkha earthquake, specifically by the main shock, was slightly more than the expected number of landslides for the recorded maximum peak ground acceleration (PGA) in comparison to the co-seismic landslides triggered by 26 earthquakes. Over 90% of those moderate- to large-scale landslides were concentrated within the estimated fault rupture surface. Majority of these moderate- to large-scale landslides were disrupted failures with over 96% of which were classified as earth falls. However, the majority of small-scale landslides were rock or boulder falls. The most number of moderate- to large-scale landslides were triggered in the slate, shale, siltstone, phyllite, and schist of the Lesser Himalayan formation followed by an equally significant number in both schist, gneiss, etc. of the Higher Himalayan formation and the phyllite, metasandstone, schist, etc. of the Lesser Himalayan formation. The sizes (i.e., areas) of the landslides were lognormally distributed, with a mode area of 322.0 m². Slope inclinations of the moderate- to large-scale landslides followed a normal distribution with a mean slope inclination of 32.6° and standard deviation of 13.5°. There exists a strong correlation between the number of landslides and the peak ground acceleration within the study area, specific for different geological formations.     

Geometrical characteristics of earthquake-induced landslides and correlations with control factors: a case study of the 2013 Minxian,Gansu, China, <Emphasis Type="Italic">Mw</Emphasis> 5.9 event

Geometric parameters are useful for characterizing earthquake-triggered landslides. This paper presents a detailed statistical analysis on this issue using the landslide inventory of the 2013, Minxian, China Mw 5.9 earthquake. Based on GIS software and a 5-m resolution DEM, geometric parameters of 635 coseismic landslides (with areas larger than 500 m²) were obtained, including height, length, width, reach angle (arc tangent of the height-length ratio), and aspect ratio (length-width ratio). The fitting relationship of height and length from these data is H = 0.6164L + 0.4589, with an average reach angle of 31.65°. The landslide aspect ratios concentrate in the range of 1.4～2.6, with an average of 2.11. According to the plane geometric shapes and aspect ratios, the landslides are classified into four categories: transverse landslide (LA1, L/W ≤ 0.8), isometric landslide (LA2, 0.8 < L/W ≤ 1.2), longitudinal landslide (LA3, 1.2 < L/W ≤ 3), and elongated landslide (LA4, L/W > 3). Statistics of these four types of landslides versus ten classified control factors (elevation, slope angle, slope aspect, curvature, slope position, distance to drainages, lithology, seismic intensity, peak ground acceleration, and distance to seismogenic fault) are used to examine their possible correlations and the landslide-prone areas, which would be helpful to the landslide disaster mitigation in the affected area.     

Evaluating the susceptibility of landslide landforms in Japan using slope stability analysis: a case study of the 2016 Kumamoto earthquake

This study analyzed 267 landslide landforms (LLs) in the Kumamoto area of Japan from the database of about 0.4 million LLs for the whole of Japan identified from aerial photos by the National Research Institute for Earth Science and Disaster Resilience of Japan (NIED). Each LL in the inventory is composed of a scarp and a moving mass. Since landslides are prone to reactivation, it is important to evaluate the sliding-recurrence susceptibility of LLs. One possible approach to evaluate the susceptibility of LLs is slope stability analysis. A previous study found a good correlation (R ² = 0.99) between the safety factor (F _s ) and slope angle (α) of F _s  = 17.3α ^?0.843. We applied the equation to the analysis of F _s for 267 LLs in the area affected by the 2016 Kumamoto earthquake (M _j  = 7.3). The F _s was calculated for the following three cases of failure: scarps only, moving mass only, and scarps and moving mass together. Verification with the 2016 Kumamoto earthquake event shows that the most appropriate method for the evaluation of LLs is to consider the failure of scarps and moving mass together. In addition, by analyzing the relationship between the factors of slope of entire landslide and slope of scarp for LLs and comparing the results with the Aso-ohashi landslide, the largest landslide caused by the 2016 Kumamoto earthquake, we also found that morphometric analysis of LLs is useful for forecasting the travel distance of future landslides.     

Crystal chemistry of selenates with mineral-like structures. III. Heteropolyhedral chains in the crystal structure of [Mg(H<Subscript>2</Subscript>O)<Subscript>4</Subscript>(SeO<Subscript>4</Subscript>)]<Subscript>2</Subscript>(H<Subscript>2</Subscript>O)

The crystal structure of a new compound [Mg(H₂O)₄(SeO₄)]₂(H₂O) (monoclinic, P2 ₁/a, a = 7.2549(12), b = 20.059(5), c = 10.3934(17) Å, β = 101.989(13), V = 1479.5(5) ų) has been solved by direct methods and refined to R ₁ = 0.059 for 2577 observed reflections with |F _hkl | ≥ 4σ|F _hkl |. The structure consists of [Mg(H₂O)₄(SeO₄)]⁰ chains formed by alternating corner-sharing Mg octahedrons and (SeO₄)^2? tetrahedrons. O atoms of Mg octahedrons that are shared with selenate tetrahedrons are in a trans orientation. The heteropoly-hedral octahedral-tetrahedral chains are parallel to the c axis and undulate within the (010) plane. The adjacent chains are linked by hydrogen bonds involving H₂O molecules not bound with M²⁺ cations.     

The crystal structure of alumoklyuchevskite,K<Subscript>3</Subscript>Cu<Subscript>3</Subscript>AlO<Subscript>2</Subscript>(SO<Subscript>4</Subscript>)<Subscript>4</Subscript>

The crystal structure of the unstable mineral alumoklyuchevskite K₃Cu₃AlO₂(SO₄)₄ [monoclinic, I2, a = 18.772(7), b = 4.967(2), c = 18.468(7) Å, β = 101.66(1)°, V = 1686(1) Å] was refined to R ₁ = 0.131 for 2450 unique reflections with F ≥ 4σF _hkl. The structure is based on oxocentered tetrahedrons (OAlCu ₃ ⁷⁺ ) linked into chains via edges. Each chain is surrounded by SO₄ tetrahedrons forming a structural complex. Each complex is elongated along the b axis. This type of crystal structure was also found in other fumarole minerals of the Great Tolbachik Fissure Eruption (GTFE, Kamchatka Peninsula, Russia, 1975–1976), klyuchevskite, K₃Cu₃Fe³⁺O₂(SO₄)₄; and piypite, K₂Cu₂O(SO₄)₂.     

Elastic behavior of vanadinite,Pb<Subscript>10</Subscript>(VO<Subscript>4</Subscript>)<Subscript>6</Subscript>Cl<Subscript>2</Subscript>, a microporous non-zeolitic mineral

The high-pressure behavior of a vanadinite (Pb₁₀(VO₄)₆Cl₂, a = b = 10.3254(5), c = 7.3450(4) Å, space group P6₃/m), a natural microporous mineral, has been investigated using in-situ HP-synchrotron X-ray powder diffraction up to 7.67 GPa with a diamond anvil cell under hydrostatic conditions. No phase transition has been observed within the pressure range investigated. Axial and volume isothermal Equations of State (EoS) of vanadinite were determined. Fitting the P–V data with a third-order Birch-Murnaghan (BM) EoS, using the data weighted by the uncertainties in P and V, we obtained: V ₀ = 681(1) Å³, K ₀ = 41(5) GPa, and K′ = 12.5(2.5). The evolution of the lattice constants with P shows a strong anisotropic compression pattern. The axial bulk moduli were calculated with a third-order “linearized” BM-EoS. The EoS parameters are: a ₀ = 10.3302(2) Å, K ₀(a) = 35(2) GPa and K′(a) = 10(1) for the a-axis; c ₀ = 7.3520(3) Å, K ₀(c) = 98(4) GPa, and K′(c) = 9(2) for the c-axis (K ₀(a):K ₀(c) = 1:2.80). Axial and volume Eulerian-finite strain (fe) at different normalized stress (Fe) were calculated. The weighted linear regression through the data points yields the following intercept values: Fe _a (0) = 35(2) GPa for the a-axis, Fe _c (0) = 98(4) GPa for the c-axis and Fe _V (0) = 45(2) GPa for the unit-cell volume. The slope of the regression lines gives rise to K′ values of 10(1) for the a-axis, 9(2) for the c-axis and 11(1) for the unit cell-volume. A comparison between the HP-elastic response of vanadinite and the iso-structural apatite is carried out. The possible reasons of the elastic anisotropy are discussed.     

Compressibility of strontium orthophosphate Sr<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript> at high pressure

High pressure in situ synchrotron X-ray diffraction experiment of strontium orthophosphate Sr₃(PO₄)₂ has been carried out to 20.0 GPa at room temperature using multianvil apparatus. Fitting a third-order Birch–Murnaghan equation of state to the P–V data yields a volume of V ₀ = 498.0 ± 0.1 Å³, an isothermal bulk modulus of K _T  = 89.5 ± 1.7 GPa, and first pressure derivative of K _T ′ = 6.57 ± 0.34. If K _T ′ is fixed at 4, K _T is obtained as 104.4 ± 1.2 GPa. Analysis of axial compressible modulus shows that the a-axis (K _a  = 79.6 ± 3.2 GPa) is more compressible than the c-axis (K _c  = 116.4 ± 4.3 GPa). Based on the high pressure Raman spectroscopic results, the mode Grüneisen parameters are determined and the average mode Grüneisen parameter of PO₄ vibrations of Sr₃(PO₄)₂ is calculated to be 0.30(2).     

Nature of the macroseismic paradox of the deep-focus earthquake in the Sea of Okhotsk on May 24, 2013 (<Emphasis Type="Italic">M</Emphasis> <Subscript> <Emphasis Type="Italic">w</Emphasis> </Subscript> = 8.3)

We analyzed macroseismic data and considered the effect of extremely long range propagation of sensible shocks during the deep-focus earthquake in the Sea of Okhotsk on May 24, 2013 (M_w = 8.3). In order to explain this effect, we formulated and qualitatively solved the problem of superposition of P-waves over the radial mode ₀S₀ of the natural oscillations of the Earth during this earthquake. Our results confirmed the possibility of such an interpretation of the observed macroseismic effect and also allowed us to explain the fact of anomalously low decay of seismic disturbances with distance.     

Pressure induced phase transition in Pb<Subscript>6</Subscript>Bi<Subscript>2</Subscript>S<Subscript>9</Subscript>

The crystal structure of Pb₆Bi₂S₉ is investigated at pressures between 0 and 5.6 GPa with X-ray diffraction on single-crystals. The pressure is applied using diamond anvil cells. Heyrovskyite (Bbmm, a = 13.719(4) Å, b = 31.393(9) Å, c = 4.1319(10) Å, Z = 4) is the stable phase of Pb₆Bi₂S₉ at ambient conditions and is built from distorted moduli of PbS-archetype structure with a low stereochemical activity of the Pb²⁺ and Bi³⁺ lone electron pairs. Heyrovskyite is stable until at least 3.9 GPa and a first-order phase transition occurs between 3.9 and 4.8 GPa. A single-crystal is retained after the reversible phase transition despite an anisotropic contraction of the unit cell and a volume decrease of 4.2%. The crystal structure of the high pressure phase, β-Pb₆Bi₂S₉, is solved in Pna2 ₁ (a = 25.302(7) Å, b = 30.819(9) Å, c = 4.0640(13) Å, Z = 8) from synchrotron data at 5.06 GPa. This structure consists of two types of moduli with SnS/TlI-archetype structure in which the Pb and Bi lone pairs are strongly expressed. The mechanism of the phase transition is described in detail and the results are compared to the closely related phase transition in Pb₃Bi₂S₆ (lillianite).     

Zinclipscombite,ZnFe<Stack><Subscript>2</Subscript><Superscript>3+</Superscript></Stack>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>(OH)<Subscript>2</Subscript>, a new mineral species

Zinclipscombite, a new mineral species, has been found together with apophyllite, quartz, barite, jarosite, plumbojarosite, turquoise, and calcite at the Silver Coin mine, Edna Mountains, Valmy, Humboldt County, Nevada, United States. The new mineral forms spheroidal, fibrous segregations; the thickness of the fibers, which extend along the c axis, reaches 20 μm, and the diameter of spherulites is up to 2.5 mm. The color is dark green to brown with a light green to beige streak and a vitreous luster. The mineral is translucent. The Mohs hardness is 5. Zinclipscombite is brittle; cleavage is not observed; fracture is uneven. The density is 3.65(4) g/cm³ measured by hydrostatic weighing and 3.727 g/cm³ calculated from X-ray powder data. The frequencies of absorption bands in the infrared spectrum of zinclipscombite are (cm^?1; the frequencies of the strongest bands are underlined; sh, shoulder; w, weak band) 3535, 3330sh, 3260, 1625w, 1530w, 1068, 1047, 1022, 970sh, 768w, 684w, 609, 502, and 460. The Mössbauer spectrum of zinclipscombite contains only a doublet corresponding to Fe³⁺ with sixfold coordination and a quadrupole splitting of 0.562 mm/s; Fe²⁺ is absent. The mineral is optically uniaxial and positive, ω = 1.755(5), ? = 1.795(5). Zinclipscombite is pleochroic, from bright green to blue-green on X and light greenish brown on Z (X > Z). Chemical composition (electron microprobe, average of five point analyses, wt %): CaO 0.30, ZnO 15.90, Al₂O₃ 4.77, Fe₂O₃ 35.14, P₂O₅ 33.86, As₂O₅ 4.05, H₂O (determined by the Penfield method) 4.94, total 98.96. The empirical formula calculated on the basis of (PO₄,AsO₄)₂ is (Zn_0.76Ca_0.02)_Σ0.78(Fe _1.72 ³⁺ Al_0.36)_Σ2.08[(PO₄)_1.86(AsO₄)_0.14]_Σ2.00(OH)_{1. 80} · 0.17H₂O. The simplified formula is ZnFe ₂ ³⁺ (PO₄)₂(OH)₂. Zinclipscombite is tetragonal, space group P4₃2₁2 or P4₁2₁2; a = 7.242(2) Å, c = 13.125(5) Å, V = 688.4(5) ų, Z = 4. The strongest reflections in the X-ray powder diffraction pattern (d, (I, %) ((hkl)) are 4.79(80)(111), 3.32(100)(113), 3.21(60)(210), 2.602(45)(213), 2.299(40)(214), 2.049(40)(106), 1.663(45)(226), 1.605(50)(421, 108). Zinclipscombite is an analogue of lipscombite, Fe²⁺Fe ₂ ³⁺ (PO₄)₂(OH)₂ (tetragonal), with Zn instead of Fe²⁺. The mineral is named for its chemical composition, the Zn-dominant analogue of lipscombite. The type material of zinclipscombite is deposited in the Mineralogical Collection of the Technische Universität Bergakademie Freiberg, Germany.     

Crystal chemistry of selenates with mineral-like structures: VIII. Butlerite chains in the structure of K(UO<Subscript>2</Subscript>)(SeO<Subscript>4</Subscript>)(OH)(H<Subscript>2</Subscript>O)

A new potassium uranyl selenate compound K(UO₂)(SeO₄)(OH)(H₂O) has been synthesized for the first time using the technique of evaporation from water solution. Its crystal structure has been solved by direct methods (monoclinic, P2₁/c,a = 8.0413(9) Å, b = 8.0362(9) Å, c = 11.6032(14) Å, β = 106.925(2)°, V = 717.34(14) ų) and refined to R ₁ = 0.0319 (wR ₂ = 0.0824) for 1285 reflections with |F ₀| > 4σ _F . The structure consists of [(UO₂(SeO₄)(OH)(H₂O)]^? chains extending along axis b. In the chains, the uranyl pentagonal bipyramids are linked via bridged hydroxyl anions and tetrahedral oxoanions [SeO₄]^2?. Potassium ions are situated between these chains. No chains of that type have been observed in uranyl compounds earlier, but they had been detected in the structures of butlerite, parabutlerite, uklonskovite, fibroferrite, and a number of synthetic compounds.     

Oxyvanite,V<Subscript>3</Subscript>O<Subscript>5</Subscript>, a new mineral species and the oxyvanite-berdesinskiite V<Subscript>2</Subscript>TiO<Subscript>5</Subscript> series from metamorphic rocks of the Slyudyanka Complex,southern Baikal region

Oxyvanite has been identified as an accessory mineral in Cr-V-bearing quartz-diopside meta- morphic rocks of the Slyudyanka Complex in the southern Baikal region, Russia. The new mineral was named after constituents of its ideal formula (oxygen and vanadium). Quartz, Cr-V-bearing tremolite and micas, calcite, clinopyroxenes of the diopside-kosmochlor-natalyite series, Cr-bearing goldmanite, eskolaite-karelianite dravite-vanadiumdravite, V-bearing titanite, ilmenite, and rutile, berdesinskiite, schreyerite, plagioclase, scapolite, barite, zircon, and unnamed U-Ti-V-Cr phases are associated minerals. Oxyvanite occurs as anhedral grains up to 0.1–0.15 mm in size, without visible cleavage and parting. The new mineral is brittle, with conchoidal fracture. Observed by the naked eye, the mineral is black, with black streak and resinous luster. The microhardness (VHN) is 1064–1266 kg/mm² (load 30 g), and the mean value is 1180 kg/mm². The Mohs hardness is about 7.0–7.5. The calculated density is 4.66(2) g/cm³. The color of oxyvanite is pale cream in reflected light, without internal reflections. The measured reflectance in air is as follows (λ, nm-R, %): 440-17.8; 460-18; 480-18.2; 520-18.6; 520-18.6; 540-18.8; 560-18.9; 580-19; 600-19.1; 620-19.2; 640-19.3; 660-19.4; 680-19.5; 700-19.7. Oxyvanite is monoclinic, space group C2/c; the unit-cell dimensions are a = 10.03(2), b = 5.050(1), c = 7.000(1) Å, β = 111.14(1)°, V = 330.76(5)ų, Z = 4. The strongest reflections in the X-ray powder pattern [d, Å, (I in 5-number scale)(hkl)] are 3.28 (5) (20\(\bar 2\)); 2.88 (5) (11\(\bar 2\)); 2.65, (5) (310); 2.44 (5) (112); 1.717 (5) (42\(\bar 2\)); 1.633 (5) (31\(\bar 4\)); 1.446 (4) (33\(\bar 2\)); 1.379 (5) (422). The chemical composition (electron microprobe, average of six point analyses, wt %): 14.04 TiO₂, 73.13 V₂O₃ (53.97 V₂O_3calc, 21.25 VO_2calc), 10.76 Cr₂O₃, 0.04 Fe₂O₃, 0.01 Al₂O₃, 0.02 MgO, total is 100.03. The empirical formula is (V _1.70 ³⁺ Cr_0.30)_2.0(V _0.59 ⁴⁺ Ti_0.41)_1.0O₅. Oxyvanite is the end member of the oxyvanite-berdesinskiite series with homovalent isomorphic substitution of V⁴⁺ for Ti. The type material has been deposited at the Fersman Mineralogical Museum, Russian Academy of Sciences, Moscow.     

Crystal chemistry of natural and synthetic lead oxyhalides. Part I. Crystal structure of Pb<Subscript>13</Subscript>O<Subscript>10</Subscript>Cl<Subscript>6</Subscript>

Crystals of lead oxychloride Pb₁₃O₁₀Cl₆ have been synthesized on the basis of high-temperature solid-state reactions. The Pb₁₃O₁₀Cl₆ structure was studied using X-ray single-crystal diffraction analysis. The compound is monoclinic, and the space group is C2/c; the unit-cell dimensions are a = 16.1699(14), b = 7.0086(6), c = 23.578(2) Å, β = 97.75°, and V = 2647.6(4) ų. The structure has been solved by direct methods and refined to R ₁ = 0.0505 for 2671 observed unique reflections. The structure is a 3D framework consisting of OPb₄ tetrahedrons. Chlorine atoms are located in the framework channels. The structure contains seven symmetrically independent Pb atoms, which are coordinated by 2 to 4 O^2? and 2 to 4 Cl^? anions. The synthesized compound is compared with other natural and synthetic lead oxyhalides.     

Stability at high-pressure,elastic behaviour and pressure-induced structural evolution of CsAlSi<Subscript>5</Subscript>O<Subscript>12</Subscript>, a potential host for nuclear waste

The elastic and structural behaviour of the synthetic zeolite CsAlSi₅O₁₂ (a = 16.753(4), b = 13.797(3) and c = 5.0235(17) Å, space group Ama2, Z = 2) were investigated up to 8.5 GPa by in situ single-crystal X-ray diffraction with a diamond anvil cell under hydrostatic conditions. No phase-transition occurs within the P-range investigated. Fitting the volume data with a third-order Birch–Murnaghan equation-of-state gives: V ₀ = 1,155(4) ų, K _T0 = 20(1) GPa and K′ = 6.5(7). The “axial moduli” were calculated with a third-order “linearized” BM-EoS, substituting the cube of the individual lattice parameter (a ³, b ³, c ³) for the volume. The refined axial-EoS parameters are: a ₀ = 16.701(44) Å, K _T0a = 14(2) GPa (β_a = 0.024(3) GPa^?1), K′ _a = 6.2(8) for the a-axis; b ₀ = 13.778(20) Å, K _T0b = 21(3) GPa (β_b = 0.016(2) GPa^?1), K′ _b = 10(2) for the b-axis; c ₀ = 5.018(7) Å, K _T0c = 33(3) GPa (β_c = 0.010(1) GPa^?1), K′ _c = 3.2(8) for the c-axis (K _T0a:K _T0b:K _T0c = 1:1.50:2.36). The HP-crystal structure evolution was studied on the basis of several structural refinements at different pressures: 0.0001 GPa (with crystal in DAC without any pressure medium), 1.58(3), 1.75(4), 1.94(6), 3.25(4), 4.69(5), 7.36(6), 8.45(5) and 0.0001 GPa (after decompression). The main deformation mechanisms at high-pressure are basically driven by tetrahedral tilting, the tetrahedra behaving as rigid-units. A change in the compressional mechanisms was observed at P ≤ 2 GPa. The P-induced structural rearrangement up to 8.5 GPa is completely reversible. The high thermo-elastic stability of CsAlSi₅O_12, the immobility of Cs at HT/HP-conditions, the preservation of crystallinity at least up to 8.5 GPa and 1,000°C in elastic regime and the extremely low leaching rate of Cs from CsAlSi₅O₁₂ allow to consider this open-framework silicate as functional material potentially usable for fixation and deposition of Cs radioisotopes.     

Synthesis,TEM characterization and thermal behaviour of LiNiSi<Subscript>2</Subscript>O<Subscript>6</Subscript> pyroxene

A pyroxene with composition LiNiSi₂O₆ was synthesized at T = 1,473 K and P = 2.0 GPa; the cell parameters at T = 298 K are a = 9.4169(6) Å, b = 8.4465(7) Å, c = 5.2464(3) Å, β = 110.534(6)°, V = 390.78(3) Å³. TEM examination of the LiNiSi₂O₆ pyroxene showed the presence of h + k odd reflections indicative of a primitive lattice, and of antiphase domains obtained by dark field imaging of the h + k odd reflections. A HT in situ investigation was performed by examining TEM selected area diffraction patterns collected at high temperature and synchrotron radiation powder diffraction. In HTTEM the LiNiSi₂O₆ was examined together with LiCrSi₂O₆ pyroxene. In LiCrSi₂O₆ the h + k odd critical reflections disappear at about 340 K; they are sharp up to the transition temperature and do not change their shape until they disappear. In LiNiSi₂O₆ the h + k odd reflections are present up to sample deterioration at 650 K. A high temperature synchrotron radiation powder diffraction investigation was performed on LiNiSi₂O₆ between 298 and 773 K. The analysis of critical reflections and of changes in cell parameters shows that the space group is P-centred up to the highest temperature. The comparative analysis of the thermal and spontaneous strain contributions in P2₁/c and C2/c pyroxenes indicates that the high temperature strain in P-LiNiSi₂O₆ is very similar to that due to thermal strain only in C2/c spodumene and that a spontaneous strain contribution related to pre-transition features is not apparent in LiNiSi₂O₆. A different high-temperature behaviour in LiNiSi₂O₆ with respect to other pyroxenes is suggested, possibly in relation with the presence of Jahn–Teller distortion of the M1 polyhedron centred by low-spin Ni³⁺.     

Single-crystal structure and Raman spectroscopy of synthetic titanite analog CaAlSiO<Subscript>4</Subscript>F

Synthetic CaAlSiO₄F, the Al-F analog of titanite, has been investigated using single-crystal synchrotron diffraction experiments at Beamline X06DA (Swiss Light Source, Paul Scherrer Institute, Villigen, Switzerland) and Raman spectroscopy. The presented structural model with 40 parameters was refined against 506 unique reflections to a final R _{o b s} of 0.026 (space group A2/a, a = 6.9120(11), b = 8.5010(10), c = 6.435(2) Å, β = 114.670(11)°, and Z = 4) and exhibits less distorted coordination polyhedra than earlier models from powder data. Vibrational spectra were calculated in harmonic approximation at the Γ point from fully relaxed energy optimisations of the crystal structure, using 3D-periodic density functional theory with Gaussian basis sets and the software CRYSTAL06. The lattice parameters of the fully relaxed structure were in good agreement with the experimental values, with the calculated values 0.8 ± 0.4 % too large; the monoclinic angle was calculated 0.4° too large. The agreement of the calculated Raman frequencies with the observed ones was very good, with standard deviation ±3 cm^?1 and maximum deviations of ±7 cm^?1. Furthermore, a detailed discussion of the atomic displacements associated with each Raman mode is given.     

Equation of state of synthetic qandilite Mg<Subscript>2</Subscript>TiO<Subscript>4</Subscript> at ambient temperature

Using a diamond-anvil cell and synchrotron X-ray diffraction, the compressional behavior of a synthetic qandilite Mg_2.00(1)Ti_1.00(1)O₄ has been investigated up to about 14.9 GPa at 300 K. The pressure–volume data fitted to the third-order Birch–Murnaghan equation of state yield an isothermal bulk modulus (K _T0) of 175(5) GPa, with its first derivative \(K_{T0}^{{\prime }}\) attaining 3.5(7). If \(K_{T0}^{{\prime }}\) is fixed as 4, the K _T0 value is 172(1) GPa. This value is substantially larger than the value of the adiabatic bulk modulus (K _S0) previously determined by an ultrasonic pulse echo method (152(7) GPa; Liebermann et al. in Geophys J Int 50:553–586, 1977), but in general agreement with the K _T0 empirically estimated on the basis of crystal chemical systematics (169 GPa; Hazen and Yang in Am Miner 84:1956–1960, 1999). Compared to the K _T0 values of the ulvöspinel (Fe₂TiO₄; ~148(4) GPa with \(K_{T0}^{{\prime }} = 4\)) and the ringwoodite solid solutions along the Mg₂SiO₄–Fe₂SiO₄ join, our finding suggests that the substitution of Mg²⁺ for Fe²⁺ on the T sites of the 4–2 spinels can have more significant effect on the K _T0 than that on the M sites.     

Crystal chemistry of selenates with mineral-like structures. IV. Crystal structure of Zn(SeO<Subscript>4</Subscript>)(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>, a new compound with a mixed framework of the variscite type

The crystal structure of a new compound Zn(SeO₄)(H₂O)₂ (orthorhombic, Pbca, a = 9.0411(13), b = 10.246(2), c = 10.3318(15) Å, V = 957.1(3) ų) has been solved by direct methods and refined to R ₁ = 0.033 on the basis of 1076 observed reflections with |F _hkl | ≥ 4σ|F _hkl |. The structure contains one independent Zn²⁺ cation coordinated by two water molecules and four oxygen atoms of selenate group. The only independent (SeO₄)^2? tetrahedral oxoanion is tetradentate, sharing its corners with four adjacent [Zn²⁺O₂(H₂O₄)]²⁺ octahedrons. The structure can be described as consisting of heteropolyhedral sheets parallel to the (001) plane and linked together into a three-dimensional network. The compound belongs to the variscite structure type and is the first structurally characterized selenate of this group.     

Thermoelastic properties of chromium oxide Cr<Subscript>2</Subscript>O<Subscript>3</Subscript> (eskolaite) at high pressures and temperatures

A new synchrotron X-ray diffraction study of chromium oxide Cr₂O₃ (eskolaite) with the corundum-type structure has been carried out in a Kawai-type multi-anvil apparatus to pressure of 15 GPa and temperatures of 1873 K. Fitting the Birch–Murnaghan equation of state (EoS) with the present data up to 15 GPa yielded: bulk modulus (K _0,T0), 206 ± 4 GPa; its pressure derivative K′_0,T , 4.4 ± 0.8; (?K _0,T /?T) = ?0.037 ± 0.006 GPa K^?1; a = 2.98 ± 0.14 × 10^?5 K^?1 and b = 0.47 ± 0.28 × 10^?8 K^?2, where α _0,T  = a + bT is the volumetric thermal expansion coefficient. The thermal expansion of Cr₂O₃ was additionally measured at the high-temperature powder diffraction experiment at ambient pressure and α _0,T0 was determined to be 2.95 × 10^?5 K^?1. The results indicate that coefficient of the thermal expansion calculated from the EoS appeared to be high-precision because it is consistent with the data obtained at 1 atm. However, our results contradict α ₀ value suggested by Rigby et al. (Brit Ceram Trans J 45:137–148, 1946) widely used in many physical and geological databases. Fitting the Mie–Grüneisen–Debye EoS with the present ambient and high-pressure data yielded the following parameters: K _0,T0 = 205 ± 3 GPa, K′_0,T  = 4.0, Grüneisen parameter (γ ₀) = 1.42 ± 0.80, q = 1.82 ± 0.56. The thermoelastic parameters indicate that Cr₂O₃ undergoes near isotropic compression at room and high temperatures up to 15 GPa. Cr₂O₃ is shown to be stable in this pressure range and adopts the corundum-type structure. Using obtained thermoelastic parameters, we calculated the reaction boundary of knorringite formation from enstatite and eskolaite. The Clapeyron slope (with \({\text{d}}P/{\text{d}}T = - 0.014\) GPa/K) was found to be consistent with experimental data.