On the elastic behaviour of zeolite mordenite: a synchrotron powder diffraction study

The high-pressure elastic behaviour of a synthetic zeolite mordenite, Na₆Al_6.02Si_42.02O₉₆·19H₂O [a=18.131(2), b=20.507(2), c=7.5221(5) Å, space group Cmc2₁], has been investigated by means of in situ synchrotron X-ray powder diffraction up to 5.68 GPa. No phase transition has been observed within the pressure range investigated. Axial and volume bulk moduli have been calculated using a truncated second-order Birch–Murnaghan equation-of-state (II-BM-EoS). The refined elastic parameters are: V ₀=2801(11) ų, K _T0= 41(2) GPa for the unit-cell volume; a ₀=18.138(32) Å, K _T0(a)=70(8) GPa for the a-axis; b ₀=20.517(35) Å, K _T0(b)=29(2) GPa for the b-axis and c ₀=7.531(5) Å, K _T0(c)=38(1) GPa for the c-axis [K _T0(a): K _T0(b): K _T0(c)=2.41:1.00:1.31]. Axial and volume Eulerian finite strain versus “normalized stress” plots (fe–Fe plot) show an almost linear trend and the weighted linear regression through the data points yields the following intercept values: Fe(0)=39(4) GPa for V; Fe _a (0)=65(18) GPa for a; Fe _b (0)=28(3) GPa for b; Fe _c (0)=38(2) GPa for c. The magnitudes of the principal Lagrangian unit-strain coefficients, between 0.47 GPa (the lowest HP-data point) and each measured P>0.47 GPa, were calculated. The unit-strain ellipsoid is oriented with ε₁ || b, ε₂ || c, ε₃ || a and |ε₁|> |ε₂|> |ε₃|. Between 0.47 and 5.68 GPa the relationship between the unit-strain coefficient is ε₁: ε₂: ε₃=2.16:1.81:1.00. The reasons of the elastic anisotropy are discussed.An erratum to this article can be found at     

Structural evolution of zeolite levyne under hydrostatic and non-hydrostatic pressure: geometric modelling

This is an exploratory study on the high-pressure (HP) structural evolution of a zeolitic framework (with LEV topology) on the basis of geometric modelling and previously published accurate unit-cell constants measured by means of single-crystal X-ray diffraction. The geometric simulations for 11 P values from 0 to 5 GPa gives more insight into the HP-behaviour of levyne, showing that the anomalous elastic behaviour of this zeolite observed under hydrostatic conditions at low P (P<1 GPa) is due to a double change in the compressional mechanism. Since the geometric simulation is not restricted to using the experimentally determined cell parameters, simulations of uniaxial compression along the [001] direction and of compression in the (001) plane have been performed, shedding more light on the compression mechanisms under non-hydrostatic regimes, which are difficult to access experimentally. The mechanisms associated with compressions along different axes provide insight into the hydrostatic compression mechanisms leading to the anomalous elastic behaviour.Electronic Supplementary Material Supplementary material is available for this article at and is accessible for authorized users.     

High-pressure X-ray and Raman study of a ferrian magnesian spodumene

The high-pressure behaviour of a synthetic P2₁/c ferrian magnesian spodumene, ^M2 (Li_0.85Mg_0.09Fe²⁺ _0.06)^M1(Fe³⁺ _0.85Mg_0.15)Si₂O₆, has been investigated using in situ single-crystal X-ray diffraction and Raman spectroscopy. No phase transition has been observed within the pressure range investigated. The isothermal equation of state up to 7 GPa was determined. V₀, K_T0 and K, simultaneously refined with a Murnaghan equation of state, are: V₀= 415.66(7) ų, K_T0=83(1) GPa and K=9.6(6). The magnitudes of the principal unit-strain coefficients were calculated and their ratios 1:2:3=1.00:1.85:2.81 at P=6.83 GPa indicate a very strong anisotropy. Monitoring of the intensity of b-type reflections (h+k= 2n+1) confirms that from room conditions up to 7 GPa the primitive lattice is maintained. Raman spectra have been collected up to 7.4 GPa. No change in the number of observed vibrational modes occurs in the pressure range investigated. At high frequency, the Raman doublet relative to the Si–O–Si vibrations of the two distinct tetrahedral chains is a broad band at room pressure, however, the frequency difference between the two modes increases with increasing pressure.Operating system: Windows NT     

Structural and vibrational behaviour of fluorapatite with pressure. Part I: in situ single-crystal X-ray diffraction investigation

Using single-crystal X-ray diffraction from a diamond anvil cell, the compressibility of a synthetic fluorapatite was determined up to about 7?GPa. The compression pattern was anisotropic, with greater change along a than c. Unit cell parameters varied linearly with β _a =3.32(8)?10^?3 and β _c =2.40(5)?10^?3 GPa^?1, giving a ratio β _a :β _c =1.38:1. Data fitted with a third-order Birch-Murnaghan EOS yielded a bulk modulus of K ₀=93(4)?GPa with K′=5.8(1.8). The evolution of the crystal structure of fluorapatite was analysed using data collected at room pressure, at 3.04 and 4.72?GPa. The bulk modulus of phosphate tetrahedron is about three times greater than the bulk modulus of calcium polyhedra. The values were 270(10), 100(4) and 86(3) GPa for P, Ca1 (nine-coordinated) and Ca2 (seven-coordinated) respectively. While the calcium polyhedra became more regular with pressure, the distortion of the phosphate tetrahedron remained unchanged. The size of the channel extending along the [001] direction represented the most compressible direction. The Ca2–Ca2 distance decreased from 3.982 to 3.897?Å on compression from 0.0001 to 4.72?GPa. The anisotropic compressional pattern may be understood in terms of the greater compressibility of the channel size over the polyhedral units. The reduction of the channel volume was measured by the evolution of the trigonal prism, having the Ca2–Ca2–Ca2 triangle as its base and the c lattice parameter as its height. This prism volume changed from 47.3?ų at room pressure to 44.78?ų at 4.72?GPa. Its relatively high bulk moduli, 86(3) GPa, indicated that the channel did not collapse with pressure and the apatite structure could remain stable at very high pressure.     

Petrological and geochemical evolution of the Kymi stock, a topaz granite cupola within the Wiborg rapakivi batholith, Finland

The 6×3 km Kymi monzogranite stock represents the apical part of an epizonal late-stage pluton that was emplaced within the 1.65 to 1.63 Ga Wiborg rapakivi batholith. The stock has a well-developed zonal structure, from the rim to the center: stockscheider pegmatite, equigranular topaz granite, porphyritic topaz granite. The contact between the two granites is usually gradational within a few centimeters, but local inclusions of the porphyritic granite in the equigranular granite indicate that the latter solidified later. Hydrothermal greisen and quartz veins, some of which contain genthelvite, beryl, wolframite, cassiterite, and sulfides, cut the granites of the stock and the surrounding country rocks. The equigranular granite contains 1 to 4 vol.% topaz, and its biotite is lithian siderophyllite; the porphyritic granite has 0 to 3 vol.% topaz, and the mica is siderophyllite. The equigranular granite is geochemically highly evolved with elevated Li, Rb, Ga, Ta, and F, and very low Ba, Sr, Ti, and Zr. The REE patterns show deep negative Eu anomalies and tetrad effects indicating extreme magmatic fractionation and aqueous fluid–rock interaction. The zonal structure of the stock is interpreted as a result of differentiation within the magma chamber. Internal convection in the crystallizing magma chamber and upward flow of residual melt as a boundary layer along sloping contacts resulted in accumulation of a layer of highly evolved, volatile-rich magma in the apical part of the chamber. Crystallization of this apical magma produced the stockscheider pegmatite and the equigranular granite; the underlying crystal mush solidified as the porphyritic granite. Much of the crystallization took place from volatile-saturated melt, and episodic voluminous degassing expelled fluids into opened fractures where they or their derivatives reacted with country rocks and caused alteration and mineralization.     

巴里坤盆地晚古生代火山岩年代学及构造演化

与周缘相邻的含油气盆地相比,前人对巴里坤盆地的研究少之又少,对其认识也不够完善;特别是由于缺乏化石及年代学资料,对研究基础的地层划分方案也一直存在争议.本文通过LA-ICP-MS单颗粒锆石U-Pb同位素测年方法对盆内Bal井岩心取样的凝灰岩进行了年代学测定,依据测定结果并结合地震反射同相轴特征对巴里坤盆地的地层重新进行...     

Quasi-harmonic computer simulations of the structural behaviour and EOS of pyrope at high pressure and high temperature

Numerical simulations, using empirical interatomic potentials within the framework of lattice dynamics and quasi-harmonic approximation, have been carried out to model the behaviour of the structure and of some thermoelastic properties of pyrope at high pressure and high temperature conditions (0–50 GPa, 300–1500 K). Comparison with observed data, available as a function either of P or of T, suggests that the pressure effects are satisfactorily modelled, whilst the effect of T on the simulations is underestimated. The cell edge, bond lengths and polyhedral volumes have been studied as a function of P along five isotherms, spaced by 300 K steps. These isotherms tend to converge at high pressure, which demonstrates that the pressure effects become dominant compared to those of thermal origin in affecting the structural properties far from ambient conditions. The cell parameter, bond distances, and other structural and thermoelastic quantities determined through simulations have been parametrised as a function of P and T by polynomial expansions. Bulk modulus and thermal expansion have been discussed in the light of the high-temperature-Birch-Murnaghan and of the Vinet P – V – T equations of state. The predictions of the bulk modulus versus P and T from the present calculations and from the Vinet-EOS agree up to 10 GPa, but they differ at higher pressure. Received: 23 October, 1998 / Revised, accepted: 23 April, 1999     

The effect of composition and cation ordering on the compressibility of columbites up to 7 GPa

The unit-cell parameters of two columbite samples along the (Fe,Mn)Nb₂O₆ solid solution were measured by means of high-pressure single-crystal X-ray diffraction up to pressures of 7 GPa. The compressional behaviour of these minerals was studied as a function of composition and degree of order. The P–V data of all the samples were fitted with a third-order Birch–Murnaghan equation of state. For the two samples with different compositions but identical degree of order the substitution of Mn for Fe causes a decrease of the bulk modulus K _T0, from 153(1) to 146(1) GPa, without any effect on the pressure first derivative K′. For the two samples with the same composition, cation ordering causes an increase of the bulk modulus from 149(1) to 153(1) GPa and of the pressure first derivative from 4.1(2) to 4.8(3). The compressional behaviour is anisotropic with a linear axial compressibility scheme β _b > β _c ≥ β _a for all samples, regardless of composition and degree of order. Such anisotropy increases sligthly with increasing Mn content.     

东至断裂带构造变形特征及其构造演化

东至断裂带是皖西南一条重要的北北东向断裂带。详细的构造解析表明,该断裂带主要经过3期构造变形,分别是发生在晚侏罗世末—早白垩世初的左行平移断层、早白垩世期间的伸展构造和晚白垩世—新生代的右行平移断层。通过断层擦痕矢量反演和断层叠加改造关系分析,认为东至断裂带及其两侧多期构造变形对应的区域应力场分别为近南北向挤压、北北西—南南东向挤压、北西—南东向伸展和近东西向挤压应力场。东至断裂带的形成和演化与郯庐断裂带相似,主要与华南与华北板块俯冲碰撞、伊泽奈崎板块和古太平洋板块向欧亚板块俯冲碰撞与弧后扩张、及印度板块向北碰撞后产生向东的构造挤出等多构造体制共同作用有关。     

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.     

Iron-water reaction at high pressure and temperature, and hydrogen transport into the core

We observed a direct reaction of metallic iron with water to form iron hydride and iron oxide, 3Fe + H₂O–>2FeH_x + FeO, at pressures from 6 GPa to 84 GPa and temperatures above 1,000 K in diamond anvil cell (DAC). Iron hydride is dhcpFeH_x or -FeH_x, and iron oxide has the rhombohedral or B1 structure at pressures at least up to 37 GPa. The formation of an assembly composed of dhcpFeH_x and FeO with the B8 structure was observed at 84 GPa. In primordial Earth, water formed by dehydration of the low temperature primitive materials reacts with metallic iron in the high temperature component to form iron hydride FeH_x and iron oxide FeO. The former would be incorporated in the iron forming the core. Thus hydrogen could be an important element of the Earths core. This reaction would be essential for transport of hydrogen into the core in the accretion stage of the Earth.     

Pressure-induced dehydration of dioptase: A single-crystal X-ray diffraction and Raman spectroscopy study

We present a synchrotron-based, single-crystal X-ray diffraction and Raman spectroscopy study of natural green dioptase (Cu₆Si₆O₁₈·6H₂O) up to ∼30 GPa at room temperature. The lattice parameters of dioptase exhibit continuous compression behavior up to ∼14.5 GPa, whereupon a structural transition is observed. Pressure–volume data below 14.5 GPa were fitted to a second-order Birch–Murnaghan equation of state with V₀ = 1440(2) ų and K₀ = 107(2) GPa, with K₀′ = 4(fixed). The low-pressure form of dioptase exhibits anisotropic compression with axial compressibility β_a > β_c in a ratio of 1.14:1.00. Based on the diffraction data and Raman spectroscopy, the new high-pressure phase could be regarded as a dehydrated form of dioptase in the same symmetry group. Pressure-induced dehydration of dioptase contributes broadly to our understanding of the high-pressure crystal chemistry of hydrous silicates containing molecular water groups.     

库车冲断带秋里塔格构造带东段构造样式与构造演化

秋里塔格构造带位于库车褶皱冲断前缘,其东段包括东秋里塔格背斜和库车塔吾背斜。野外调查和地震剖面解释表明:秋里塔格构造带东段盐下发育断层转折褶皱; 盐上东秋里塔格背斜为滑脱箱状背斜,库车塔吾背斜核部为南倾逆冲断层所破坏。演化剖面显示秋里塔格构造带东段在侏罗纪断陷期发育了正断裂,其后为平静期,直到库车晚期后逆冲断层和褶皱快速发育,背斜最终形成。膏盐岩及古构造对构造变形具有重要影响,一方面作为滑脱层,分割了盐下层与盐上层,导致二者形成不同的构造样式; 另一方面塑性流动充填于背斜核部。由于膏盐岩的厚度差异,东秋里塔格背斜盐上发育褶皱,而库车塔吾背斜核部被逆冲断层破坏,膏盐层厚度还影响了膏盐层上下构造高点的相对位置。盐下构造的发育受侏罗纪古构造控制,进而影响了盐上构造的发育。     

海拉尔盆地乌尔逊-贝尔凹陷构造演化对油气成藏的控制作用

从成盆、成源、成烃和成藏4个方面对海拉尔盆地乌尔逊-贝尔凹陷各构造演化阶段的石油地质意义进行了分析。海拉尔盆地成盆的动力机制是中蒙边界区中生代推覆构造形成后的晚造山期伸展垮塌作用,为典型的被动裂陷盆地。乌尔逊-贝尔凹陷形成演化经历了5个时期：山间残留阶段、被动裂陷阶段、主动裂陷阶段、断坳转化阶段和坳陷阶段。被动裂陷阶段沉积物震荡式沉积形成南一段中部砂泥互层的优质烃源岩,主动裂陷阶段盆地强烈裂陷,窄而深的断陷结构控制盆地南一段上部有效源岩分布,断坳转化阶段盆地快速沉降促进烃源岩熟化,伊敏组沉积晚期烃源岩大量排烃控制形成早期原生油藏,伊敏组末期盆地反转,部分油藏受活动断裂破坏调整到大磨拐河组形成次生油藏。不同演化阶段形成多种类型的隆起带,构成有利的油气聚集区带,控制了不同含油气系统油气聚集。     

Rigid unit modes at high pressure: an explorative study of a fibrous zeolite-like framework with EDI topology

We report a comparative study on the high pressure (HP) structural behaviour of a fibrous zeolite (with EDI topology) on the basis of rigid unit modes (RUM) modelling and previously published single-crystal X-ray diffraction. HP single-crystal diffraction data lead to a more precise determination of the elastic parameters (axial and volume compressibilities) useful to define the equation-of-state under isothermal conditions, and the structural refinements are useful to describe the main deformation mechanisms of the Si/Al framework and extra-framework content at high pressure. The RUM modelling is applied to simulate the compressive behaviour of the framework, under hydrostatic and non-hydrostatic conditions, using a minimum number of parameters, and to describe the deformation mechanism intuitively in terms of the rotations of the SiO₄ polyhedra. The local and global P-induced deformation mechanisms of the Si/Al framework observed in experiment (channel ellipticity, SBU rotation) are well reproduced by RUM modelling. The simulation of uniaxial compression (non-hydrostatic conditions) shows an interesting result on the structural behaviour. This comparative study tests the reliability of the RUM modelling in open-framework silicates with a complicated crystal structure.Electronic Supplementary Material: Supplementary material to this paper is available in electronic form at     

高煤级煤—隐晶质石墨的Raman光谱表征及结构演化

拉曼光谱能够反映碳材料结构的有序程度和结构缺陷,可用来表征高煤级煤—隐晶质石墨演化过程中结构变化。通过对受岩浆热变质影响的不同变形变质程度样品的拉曼参数与面网间距（d₀₀₂）之间关系的研究表明：G峰位置与d₀₀₂呈现阶梯变化,能较好地区分出石墨与高煤级煤,S₂峰位、D₁、G半峰宽与d₀₀₂呈较好的线性关系;D₁与G峰峰位差和半峰宽比随d₀₀₂减小而减小,S₂与S₄峰的峰位差随d₀₀₂减小先增大后减小,而其强度比及面积比逐渐增大;d₀₀₂与拉曼参数关系显示两次明显的结构演化跃变,即无烟煤至变质无烟煤阶段,R_max>6.5%、P（D₁-G）<235 cm^-1、P（S₂-S₄）>525 cm^-1以及半峰宽比显著下降、L_a/L_c迅速降低,为芳构化、芳环缩合作用增强向芳环叠片拼叠转变;半石墨至石墨演化阶段,P（D₁-G）、I_D1/I_G与A_D1/A_G显著降低,L_a、L_c迅速增加。以d₀₀₂为标度能较好地反映煤结构在不同演化阶段的Raman光谱特征。     

High temperature structural and thermoelastic behaviour of mantle orthopyroxene: an in situ neutron powder diffraction study

The temperature induced structural evolution and thermoelastic behaviour of a natural (Pbca) orthopyroxene (Opx), with chemical formula ^M2(Mg_0.856Ca_0.025Fe²⁺ _0.119) ^M1(Mg_0.957Fe²⁺ _0.011Fe³⁺ _0.016Cr_0.011Al_0.005)Al_0.032Si_1.968O₆, from a suite of high pressure ultramafic nodules of mantle origin, have been investigated by in-situ neutron powder diffraction at several temperatures starting from 1,200°C down to 150°C. Unit-cell parameter variations as a function of T show no phase transition within this temperature range. The volume thermal expansion coefficient, α = V ⁻¹(∂V/∂T) _P0, varies linearly with T. The axial thermal expansion coefficients, α_j = l _j⁻¹(∂l _j/∂T)_P0, increase non-linearly with T. The principal Lagrangian unit-strain coefficients (ɛ//a, ɛ//b, ɛ//c), increase continuously with T. However, the orientation of the unit-strain ellipsoid appears to change with T. With decreasing T, the values of the unit-strain coefficients along the b and c axes tend to converge. The orientation at ΔT = 1,080°C is maintained down to the lowest temperature (150°C). The two non-equivalent tetrahedral chains, TA _n OA_3n and TB _n OB_3n , are kinked differently. At room-T, the TB _n OB_3n chain is more strongly kinked by about 23° than the TA _n OA_3n chain. With increasing T, the difference decreases by 3° for the TB _n OB_3n chain. The intersite cation exchange reaction between M1 and M2 (Mg²⁺ and Fe²⁺) shows a slight residual order at 1,200°C followed by reordering with decreasing temperature although seemingly not with a definite progressive trend. At the lowest temperature reached (150°C), reordering has occurred with the same value of partitioning coefficient K _D as that before heating. The absence of the expected phase transition is most likely due to the presence of minor amounts of Fe³⁺, Al, Ca and Cr which must play a crucial role on the thermoelastic behaviour and phase stability fields in natural Opx, with consequent important petrologic and geological implications.     

Comparative compressibility and equation of state of orthorhombic and tetragonal edingtonite

The high-pressure (HP) behaviour of a natural orthorhombic and tetragonal edingtonite from Ice River, Canada, has been investigated using in situ single-crystal X-ray diffraction. The two isothermal equations of state up to 6.74(5) GPa were determined. V₀, K_T0 and K refined with a third-order Birch–Murnaghan equation of state (BM-EoS) are: V₀ = 598.70(7) ų, K_T0 = 59(1) GPa and K=3.9(4) for orthorhombic edingtonite and V₀ = 600.9(2) ų, K_T0 = 59(1) GPa and K=4.2(5) for tetragonal edingtonite. The experiments were conducted with nominally hydrous pressure penetrating transmitting medium. No overhydration effect was observed within the pressure range investigated. At high-pressures the main deformation mechanism is represented by cooperative rotation of the secondary building unit (SBU).Si/Al distribution slightly influences the elastic behaviour of the tetrahedral framework: the SBU bulk moduli are 125(8) GPa and 111(4) GPa for orthorhombic and tetragonal edingtonite, respectively. Extra-framework contents of both zeolites show an interesting behaviour under HP conditions: the split Ba2 site at P >2.85 GPa is completely empty; only the position Ba1 is occupied. Electronic Supplementary Material. Supplementary material to this paper (Observed and calculated structure factors) is available in electronic form at Electronic Supplementary Material Supplementary material is available in the online version of this article at