Molecular modeling of the 10-Å phase at subduction zone conditions

Molecular dynamics (MD) modeling of the 10-Å phase, Mg₃Si₄O₁₀(OH)₂·xH₂O, with x=2/3, 1.0 and 2.0 shows complex structural changes with pressure, temperature and water content and provides new insight into the structures and stabilization of these phases under subduction zone conditions. The structure(s) of this phase and its role as a reservoir of water in the mantle have been controversial, and these calculations provide specific predictions that can be tested by in situ diffraction studies. At ambient conditions, the computed structures of talc (x=0) and the 10-Å phases with x=2/3 and 1.0 are stable over the 350-ps period of the MD simulations. Under these conditions, the 10-Å phases show phlogopite-like layer stacking in good agreement with previously published structures based on powder X-ray diffraction data for samples quenched from high-pressure and high-temperature experiments. The calculations show that the 10-Å phase with x=2.0 is unstable at ambient conditions. The computed structures at P=5.5 GPa and T=750 K, well within the known stability field of the 10-Å phase, change significantly with water content, reflecting changing H-bonding configurations. For x=2/3, the layer stacking is talc-like, and for x=1.0, it is phlogopite-like. The calculations show that transformation between these two stackings occurs readily, and that the talc-like stacking for the x=2/3 composition is unlikely to be quenchable to ambient conditions. For x=2.0, the layer stacking at P=5.5 GPa and T=750 K is different than any previously proposed structure for a 10-Å phase. In this structure, the neighboring basal oxygens of adjacent magnesium silicate layers are displaced by b/3 (about 3 Å) resulting in the Si atoms of one siloxane sheet being located above the center of the six-member ring across the interlayer. The water molecules are located 1.2 Å above the center of all six-member rings and accept H-bonds from the OH groups located below the rings. The b/3-displaced structure does not readily transform to either the talc-like or phlogopite-like structure, because neither of these stackings can accommodate two water molecules per formula unit. There is likely to be a compositional discontinuity and phase transition between the b/3-displaced phase and the phase with phlogopite-like stacking. The simulations reported here are the first to use the recently developed CLAYFF force field to calculate mineral structures at elevated pressures and temperatures.     

四川新康风化淋滤型海泡石的热相变研究

以四川新康风化淋滤型海泡石为研究对象，利用X射线衍射分析和红外光谱分析技术，对海泡石的热相变过程及特征进行了研究。结果发现，四川新康风化淋滤型海泡石的相变过程与沉积型、热液型海泡石相变过程明显不同，其相变过程可以划分为两个阶段：800℃以下保持海泡石相；800℃以上海泡石相转化为斜顽辉石相。     

Thermal decomposition of NH4-analcime

The thermal decomposition of ammonium-exchanged natural analcime is characterized by gas chromatography, IR spectroscopy and X-ray diffraction. The de-ammoniation and dehydroxylation proceed in parallel throughout the decomposition, which evidences the instability of the protonated analcime framework. The mechanism of degassing of NH₄-analcime changes throughout its decomposition. At the initial step, the mechanism of de-ammoniation consists in thermal dissociation of NH₄⁺ molecule onto NH₃ and proton (framework OH group) and diffusion of NH₃ out of the structure. Subsequent decomposition and removal of the OH groups lead to a progressive loss of crystallinity. At this step, an apparent activation energy for NH₃ desorption is estimated to be 145(±13) kJ mol^–1. This value is within the upper limit of the activation energy characteristic for the NH₃ desorption from proton centres in large-pore zeolites. At the final step, the adsorption of NH₃ and protons onto the defect centres in the amorphosed aluminosilicate framework results in a significant increase of an apparent activation energy for the de-ammoniation and dehydroxylation up to 270(±20) kJ mol^–1.     

The magmatic to hydrothermal transition and its bearing on ore-forming systems

The exsolution of volatile phases from silicate magmas controls physical and chemical magma properties and influences large-scale geologic phenomena and processes having major societal and economic implications including the release of climate-altering gases to the atmosphere, the explosivity of volcanic eruptions, hydrothermal alteration, and the generation of magmatic–hydrothermal mineralization. These volatile phases exsolve from a wide variety of magmas and cover a very broad spectrum of compositions.

The transition from the orthomagmatic to the hydrothermal stages has important bearing on these fundamentally important geologic phenomena, and this report summarizes the published results of a dozen scientific investigations on the magmatic–hydrothermal transition as applied to volcanic eruption and magmatic–hydrothermal mineralization. These studies involve a variety of analytical and experimental methodologies, and many focus on fluid and melt inclusions from mineralized magmatic systems. A primary goal of each study is to better understand the role of magmatic volatiles and the importance of the magmatic–hydrothermal transition on these geologic processes.     

Sorption Characteristics of Rare Earth Element Eu^3＋ onto Silica-Water Interfaces Studied by Fluorescence Spectroscopy

The sorption of Eu species onto nano-size silica-water interfaces was investigated using fluorescence spectroscopy for Ph ranges of 1-8.5 and an initial Eu concentration (Ceu) of 2×10-4 M. The sorption rate of Eu was initially low, but significantly increased at Ph>4. The sorption density of Eu species on a silica surface was ～1.58×10-7 mol/m2 when the dissolved Eu species were completely sorbed onto silica-water interfaces at Ph=～5.8. The sorbed Eu species at Ph<6 is aquo Eu3 , which is sorbed onto silica-water interfaces as an outer-sphere complex at Ph<5, but may be sorbed as an inner-sphere bidentate complex at 5相似文献   

The structural role of Ti in aluminosilicate liquids in the glass transition range: insights from heat capacity and shear viscosity measurements

The shear viscosities and 1 bar heat capacities of glasses and melts along the 67mol% silica isopleth in the system SiO₂-Al₂O₃-Na₂O-TiO₂ have been determined in the temperature ranges 780-1140 K and 305-1090 K respectively. Anomalous behaviour of both these properties is observed for compositions rich in TiO₂ and/or Al₂O₃, an observation attributed to liquid-liquid phase separation followed by anatase crystallization. For samples which do not show anomalous behaviour, it is found that the partial molar heat capacity of the TiO₂ component previously determined in Al-free compositions reproduces our heat capacities to within 1.3%. Viscosity data show that addition of TiO₂ tends to increase viscosity and melt fragility at constant temperature. Furthermore, heat capacity and viscosity data may be combined within the framework of the Adam-Gibbs theory to extract values of the configurational entropy of the liquids and qualitative estimates of the variation of the average energy barrier to viscous flow. Configurational entropy at 900K is inferred to decrease upon addition of TiO₂, in contrast to previous results from Al-free systems. The compositional limit separating normal from anomalous behaviour, as well as the data for homogenous melts have been used to constrain the structural role of Ti in these samples. Our data are consistent with a majority of Ti in five-fold coordination associated with a titanyl bond, in agreement with previous spectroscopic studies. Furthermore, we find no evidence for a Ti-Al interaction in our samples, and we are led to the conclusion that Al and Ti are incompletely mixed, a hypothesis consistent with the observed reduction of configurational entropy upon addition of TiO₂, suggesting an important role of medium range order in controlling the variations in thermodynamic properties.     

海洋平流的季节变化对La Nia事件成熟位相锁定的作用

用一个中等复杂程度的热带海气耦合模式模拟LaNi na事件成熟位相锁定在年底左右的特征并研究其形成的机制。结果表明 ,模式能很好地模拟观测到的LaNi na事件成熟位相锁定在年底左右的特征。LaNi na事件成熟位相锁定在年底主要由海洋气候基本态引起。海洋垂直平均流是LaNi na事件成熟位相锁定在年底左右的最主要因子。由海洋气候基本态的季节变化所引起的冷平流的季节变化是LaNi na事件成熟位相锁定在年底的机制。在LaNi na事件期间 ,1～ 5月份 ,赤道中东太平洋地区的冷平流较弱 ,它不能平衡海气热量交换过程的影响 ,因而海洋表面温度增加。这一过程使海气耦合不稳定度减弱 ,从而使LaNi na事件衰减。 6～ 12月份 ,赤道中东太平洋地区的冷平流较强。海气热量交换过程的影响不能平衡较强冷平流的影响 ,因而海洋表面温度减小。这一过程使海气耦合不稳定度加强 ,从而使LaNi na事件发展。这样 ,LaNi na事件成熟位相容易出现在年底左右。     

Variation of the plasma turbulence in the central plasma sheet during substorm phases observed by the interball/tail satellite

Fluctuations of the plasma bulk velocity across the plasma sheet are studied using single-point measurements from the Corall instrument on board the Interball/Tail satellite. Several hour-long intervals of continuous data corresponding to quiet geomagnetic conditions and different phases of isolated substorms are analyzed. The plasma sheet flow appears to be strongly turbulent, i.e. dominated by fluctuations that are unpredictable. Corresponding eddy diffusion coefficients were obtained as a function of the autocorrelation time and rms velocity of the fluctuations. It was found that the amplitude of the turbulence and the values of eddy-diffusion coefficients increase significantly during substorm growth and expansion phases and they decrease to their initial level during the recovery phase. We also studied a relationship between the eddy-diffusion coefficients and the absolute value of the geomagnetic field, also measured by the Interball/Tail satellite. It was found that this relationship varies depending on the phase of substorm, indicating possible change in the turbulence regimen with substorm phase.     

Experimental and theoretical study of stability of dense hydrous magnesium silicates in the deep upper mantle

Fluid-undersaturated experiments were conducted to determine the phase relations in the simplified peridotite system MgO-SiO₂-H₂O (MSH) at 11.0-14.5 GPa and 800-1400 °C. Stability relations of dense hydrous magnesium silicates (DHMSs) under fluid-undersaturated conditions were experimentally examined. From the fluid-absent experimental results, we retrieved thermodynamic data for clinohumite, phase A, phase E, and hydrous wadsleyite, consistent with the published data set for dry mantle minerals. With this new data set, we have calculated phase equilibria in the MSH system including dehydration reactions. The dehydration reactions calculated with lower water activities of 0.68-0.60 match the fluid-present experiments of this study above 11.0 GPa and 1000 °C, indicating that considerable amounts of silicate component were dissolved into the fluid phase. The calculated phase equilibria illustrate the stability of the post-antigorite phase A-bearing assemblages. In the cold subducting slab peridotite, phase A + enstatite assemblage survives into the transition zone, whereas phase A + forsterite + enstatite assemblage forms hydrous wadsleyite at a much shallower depth of about 360-km. The slab is subducted with no dehydration reactions occurring when entering the transition zone. The phase equilibria also show the high temperature stability of phase E. Phase E is stable up to 1200 °C at 13.5 GPa, a plausible condition in the mantle of relatively low temperature, i.e., beneath subduction zones. Phase E is a possible water reservoir in the mantle as well as wadsleyite and ringwoodite.