高温高压下石膏脱水相变的原位拉曼光谱研究

本文运用激光拉曼光谱仪,利用水热金刚石压腔装置对高温高压条件下石膏-水体系中的石膏脱水相变进行拉曼光谱研究。在压力0.1MPa～837.9MPa 和温度16～200℃条件下通过系列实验对相变的过程进行了原位光谱分析。与人们已知的无水条件下石膏分两步脱水的过程不同,高压下石膏在饱和水环境下倾向于一次性的脱去所有结晶水而形成无水石膏,实验中没有观察到半水石膏的出现。通过实验数据得到石膏和无水石膏的转折温度和平衡压力间的关系式为 P_(MPa)=19.56·T_(℃)-2926.5。     

俯冲带部分熔融

俯冲带是地幔对流环的下沉翼,是地球内部的重要物理与化学系统。俯冲带具有比周围地幔更低的温度,因此,一般认为俯冲板片并不会发生部分熔融,而是脱水导致上覆地幔楔发生部分熔融。但是,也有研究认为,在水化的洋壳俯冲过程中可以发生部分熔融。特别是在下列情况下,俯冲洋壳的部分熔融是俯冲带岩浆作用的重要方式。年轻的大洋岩石圈发生低角度缓慢俯冲时,洋壳物质可以发生饱和水或脱水熔融,基性岩部分熔融形成埃达克岩。太古代的俯冲带很可能具有与年轻大洋岩石圈俯冲带类似的热结构,俯冲的洋壳板片部分熔融可以形成英云闪长岩-奥长花岗岩-花岗闪长岩。平俯冲大洋高原中的基性岩可以发生部分熔融产生埃达克岩。扩张洋中脊俯冲可以导致板片窗边缘的洋壳部分熔融形成埃达克岩。与俯冲洋壳相比,俯冲的大陆地壳具有很低的水含量,较难发生部分熔融,但在超高压变质陆壳岩石的折返过程中可以经历广泛的脱水熔融。超高压变质岩在地幔深部熔融形成的熔体与地幔相互作用是碰撞造山带富钾岩浆岩的可能成因机制。碰撞造山带的加厚下地壳可经历长期的高温与高压变质和脱水熔融,形成S型花岗岩和埃达克质岩石。     

Location of OH groups and oxidation processes in triclinic chloritoid

Triclinic Fe²⁺ and Fe³⁺-chloritoid end members, as well as Fe²⁺-Fe³⁺-chloritoid solid solutions were synthesized in order to determine the location of the OH groups in the structure and to investigate the possibility of Fe³⁺ incorporation on the M1B site and the corresponding oxidation mechanism. The samples were analyzed using transmission electron microscopy, electron energy-loss and ⁵⁷Fe Mössbauer spectroscopy, polarized single-crystal, KBr powder and in situ high-pressure infrared spectroscopy. The structure of a natural triclinic chloritoid was refined by single-crystal X-ray diffraction in order to locate the proton-accepting oxygens in the triclinic structure. The results of valence bond calculations, polarized single-crystal and in situ high-pressure IR spectroscopy revealed that the orientations of the OH dipoles are the same as those in monoclinic chloritoid. The annealing experiments in air show that the incorporation of Fe³⁺ on M1B increases with temperature. After 3?h at 530?°C all Fe²⁺ was oxidized to Fe³⁺ without decomposition of the structure. This also holds true for a heating duration of 24?h. The incorporation of Fe³⁺ at M1B sites is coupled with a dehydration process starting at about 350?°C during which the H1A protons leave first.     

Thermo-optical detection of defects and decarbonation in natural smithsonite

Natural hydrothermal ZnCO₃ crystal aggregates are nominally anhydrous phases with interfacial water, with substitutional divalent cations and decarbonation c. 300°C. All these common features must be involved during the experimental heating of a thermoluminescence (TL) glow curve up to 500°C: dehydration–dehydroxylation, phase transition and ion transition of point defects in Zn²⁺ positions. A representative specimen of natural smithsonite was analysed by X-ray fluorescence spectrometry, field emission scanning electron microscopy (FESEM) with a chemical probe of energy dispersive spectrometer, high temperature in situ X-ray diffraction, differential scanning calorimetry, differential thermal analyses coupled to thermogravimetry, TL, radioluminescence and high resolution spectra thermoluminescence (3DTL), to gain an overview of the spectra emission and defects linkages modified by heating from room temperature up to 500°C. The ZnCO₃ specimen contains minor amounts of Ca, Cu, Cr, Cd, Pb, Ce, Co, Ni, Mn and Fe. Under FESEM, it displays CaCO₃ clusters and oscillatory zoning distribution with lamellae ranging from Ca_0.11Zn_0.89 to Ca_0.19Zn_0.81. The analytical results suggest assignments of defects and processes to measured 3DTL emission bands, as follows: (1) peak at ~260°C, ~360 nm bonds, breaking during the thermal decarbonation process; (2) peak ~120°C, ~340 nm: non-bridging oxygen centres associated to a complex dehydration–dehydroxylation process and (3) peak at ~170°C, ~650 nm, crystal field effects on the thermoluminescence of Mn²⁺ centres and associated transitional elements in the ZnCO₃ phase. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Hydrating laterally extensive regions of continental lithosphere by flat subduction: A pilot study from the North American Cordillera

It has been suggested that much of the lithopheric mantle beneath the Colorado Plateau was hydrated by the dehydration of the Farallon plate when it was undergoing low angle subduction during the Laramide orogeny. If correct, low angle subduction could be a viable mechanism for weakening laterally extensive regions of continental lithosphere, allowing such lithosphere potentially to be recycled back into the Earth's interior and into the asthenospheric mantle wedge. To test this hypothesis, we model the release of water during prograde metamorphism of a flat-subducting Farallon plate by considering a thermal model for flat subduction and tracking open-system metamorphic phase equilibria. Our model indicates that significant amounts of water can be laterally transported ∼700 km inboard of the trench, close to the width of the North American Cordillera. The amount of water released is shown here to have been large enough to influence the rheology of the overriding North American lithosphere and the potential for melting at its base. Anomalously high S-velocities in the lithospheric mantle supports our modeled calculations of laterally extensive weakening at the base of the continental lithosphere.     

秦岭和华北地区地壳低速层的成因探讨──岩石高温高压波速实验证据

对秦岭和华北地区地壳主要岩类１３８个样品进行高温高压实验，测量其纵波速度的结果表明，其中５４个样品出现了纵波低速现象．对出现该现象的样品的实验产物所做的肉眼和镜下观察、电子探针分析以及综合对比显示，微裂隙不是产生低速现象的决定因素，而主要是含水矿物（角闪石、黑云母等）的脱水相交和由之引发的岩石部分熔融导致岩石出现纵波低速现象．通过实验条件与中、下地壳的温度和压力等条件的类比揭示，秦岭和华北地区中、下地壳存在的低速（高导）层也可能是由含水矿物的脱水相变或岩石部分熔融引起的．     

含水氯化镁脱水方法及其对比

根据最近几十年的研究情况对目前流行的含水氯化镁脱水方法进行了分析、对比,并且介绍了他们的有关应用情况和在应用过程中的优、缺点。给出了有关热力学与动力学的最新研究成果,并对其研究前景进行了预测。     

无定形态游离氧化铁脱水老化对粘性土物理性质的影响

无定形态游离氧化铁以其自身的特性及其脱水老化作用,对粘性土的物理性质、水理性质乃至工程性质产生了一定程度的影响。本文就粘性土的物理性质、水理性质及力学性质在无定形态游离氧化铁脱水过程中的变化进行了初步研究,期望对粘性土的土工测试方法及参数的合理测定有所裨益。     

Kinetics of dehydration of Ca-montmorillonite

Isothermal thermogravimetric experiments have been carried out to determine the reaction kinetics of the dehydration processes in fuller's earth, a natural Ca-montmorillonite. Dehydration in swelling clays is a complex reaction, and analysis of the thermogravimetric data using empirical rate equations and time-transformation analysis reveals that the nature of the rate controlling mechanism is dependent upon both the temperature regime of the sample as well as the extent of reaction. For fuller's earth, we find that the dehydration kinetics are dominated by a nucleation and growth mechanism at low temperatures and fractions transformed (stage I), but above 90 °C the last stages of the reaction are diffusion controlled (stage II). The activation energy for dehydration during stage I is around 35 kJ · mol⁻¹, whereas the removal of water during stage II requires an activation energy of around 50 kJ · mol⁻¹. These two stages of dehydration are associated with primary collapse of the interlayer (stage I) and movement of water that is hydrated to cations within the interlayer (stage II). Received: 28 August 1998 / Revised, accepted: 27 January 1999     

Exploring the metamorphic consequences of secular change in the siliciclastic compositions of continental margins

Shale and greywacke compositions from the Archean to Phanerozoic record a secular change in the siliciclastic material that comprises much of Earth's continental margins, past and present. This study explores the metamorphic consequence of these compositional changes, by comparing phase equilibrium models constructed for average Archean, Proterozoic, and Phanerozoic shale and greywacke compositions equilibrated along two Barrovian-type geotherms: 1330℃/GPa(A) and 800 ℃/GPa(B). Our models show that Archean siliciclastic rocks can retain up to 4 vol.% water at middle to lower crustal conditions, nearly twice that of Proterozoic and Phanerozoic compositions. The increased ferromagnesium content of Archean siliciclastic rocks stabilizes chlorite to higher temperatures and results in a biotite-rich assemblage at solidus temperatures. Accordingly, water-absent biotite dehydration melting is predicted to play a greater role in the generation of melt in the metamorphism of Archean aged units,and water-absent muscovite dehydration melting is of increasing importance through the Proterozoic and Phanerozoic. This secular variation in predicted mineral assemblages demonstrates the care with which metamorphic facies diagrams should be applied to Archean compositions. Moreover, secular changes in the composition of shale and greywacke is reflected in the evolution of anatectic melt towards an increasingly less viscous, Ca-rich, and Mg-poor monzogranite.