A new method to calculate end-member thermodynamic properties of minerals from their constituent polyhedra II: heat capacity, compressibility and thermal expansion

Thermodynamic calculations in petrology are generally performed at pressures and temperatures beyond the standard state conditions. Accurate prediction of mineral equilibria therefore requires knowledge of the heat capacity, thermal expansion and compressibility for the minerals involved. Unfortunately, such data are not always available. In this contribution we present a data set to estimate the heat capacity, thermal expansion and compressibility of mineral end‐members from their constituent polyhedra, based on the premise that the thermodynamic properties of minerals can be described by a linear combination of the fractional properties of their constituents. As such, only the crystallography of the phase of interest needs to be known. This approach is especially powerful for hypothetical mineral end‐members and for minerals, for which the experimental determination of their thermodynamic properties is difficult. The data set consists of the properties for 35 polyhedra in the system K–Na–Ca–Li–Be–Mg–Mn–Fe–Co–Ni–Zn–Al–Ti–Si–H, determined by multiple linear regression analysis on a data set of 111 published end‐member thermodynamic properties. The large number of polyhedra determined allows calculation of a much larger variety of phases than was previously possible, and the choice of constituents together with the large number of thermodynamic input data results in estimates with associated uncertainty of generally <5%. The quality of the data appears to be sufficiently accurate for thermodynamic modelling as demonstrated by modelling the stability of margarite in the CASH system and the position of the talc–staurolite–chloritoid–pyrope absent invariant point in the KMASH system. In both cases, our results overlap within error with published equivalents.     

ISORROPIA: A New Thermodynamic Equilibrium Model for Multiphase Multicomponent Inorganic Aerosols

A computationally efficient and rigorous thermodynamic model that predicts the physical state and composition of inorganic atmospheric aerosol is presented. One of the main features of the model is the implementation of mutual deliquescence of multicomponent salt particles, which lowers the deliquescence point of the aerosol phase.The model is used to examine the behavior of four types of tropospheric aerosol (marine, urban, remote continental and non-urban continental), and the results are compared with the predictions of two other models currently in use. The results of all three models were generally in good agreement. Differences were found primarily in the mutual deliquescence humidity regions, where the new model predicted the existence of water, and the other two did not. Differences in the behavior (speciation and water absorbing properties) between the aerosol types are pointed out. The new model also needed considerably less CPU time, and always shows stability and robust convergence.     

矽线石研究及应用综述

对矽线石的成分,有主邓－无序,结构,热力学行为及应用研究进展作了综述。通过对矽线石的研究,能够为矽线石的合理利用提供理论基础,强调应堤洄强对矽线碱珠杂质成分,结构及其变化的研究。     

Impact of European Black Carbon on East Asian Summer Climate

The remote response of the East Asian summer monsoon(EASM)to European black carbon(EUBC)aerosols was studied by using an ensemble of sensitivity experiments with the Geophysical Fluid Dynamics Laboratory(GFDL)atmospheric general circulation model(AGCM)Atmospheric Model version 2.1(AM2.1).The results show that EUBC causes an enhanced EASM.The resulted enhanced southwesterly brings more moisture supply from the Bay of Bengal,which causes an increase in precipitation over the Yangtze River valley,northeastern China,the eastern part of the Yellow River valley,and the Tibetan Plateau.Diagnostic examination suggests that EUBC induces enhanced tropospheric heating over most of the Eurasian Continent through a propagating wave train and horizontal air temperature advection.This phenomenon results in intensified thermal contrast between land and ocean,which accounts for the enhanced EASM.Moreover,reductions in EUBC emission in 1992 may have contributed to decadal weakening of the EASM in the early 1990s.     

强降水过程中热力切变平流参数的诊断分析

在以往研究的基础上, 本文把对流涡度矢量的垂直分量、水平散度和广义位温的垂直梯度有机地结合起来, 引入热力切变平流参数的概念。本文针对两次强降水过程, 利用NCEP/NCAR全球最终分析资料对热力切变平流参数进行诊断分析, 结果表明, 热力切变平流参数能够比较准确地综合表征雨区上空水平风场切变和湿等熵面漏斗状向下伸展等动力学和热力学典型的垂直结构特征, 因而该参数与降水系统的发展演变密切相关, 与观测的6小时累积地面降水区存在一定的对应关系; 在空间水平分布和时间演变趋势上, 热力切变平流参数的异常值区覆盖着观测的6小时累积地面降水区; 该参数在降水区内表现为强信号, 而在非降水区表现为弱信号。影响热力切变平流参数发展演变的因素分析表明, 该参数倾向方程中通量散度项的异常值区覆盖着观测的6小时累积地面降水区, 表明雨区内通量散度项导致的热力切变平流参数变化比较明显, 其中纬向风速与经向风速相互作用的贡献是不容忽略的。     

湿热力平流参数在贵州初夏强降水中的运用

使用NCEP(1°×1°)再分析资料计算湿热力平流参数及其积分,通过对比分析2008—2009年初夏(5—6月)地面实况降水与该因子积分后的中心大值区的对应关系。理论分析表明:湿热力平流参数综合体现了锋区附近大气的动力、热力及水汽作用,相对于常用的相当位温、湿度等常用物理量来说,在一定程度上包含了广义位温及位温平流的相互作用,对实际非均匀饱和大气的动热力变化及水汽有较好的反映。统计分析也表明:积分后的湿热力平流参数中心值区与地面6小时强降水落区有较好的对应关系,它的变化趋势及移动方向与强降水区的变化也较一致,能作为短时强降水落区预报提供参考;利用NCEP/NCAR(1°×1°)再分析资料和Micaps地面实况降水资料,选取2009年6月7-9日发生在贵州的强降水过程为例,通过把湿热力平流参数与此次过程中动、热力场结合进行诊断分析,进一步表明该参数能综合地反应锋面强降水系统中的水汽、动力及热力的垂直结构特征,能作为造成强降水的锋面系统的示踪物。     

Mechanism for calcite dissolution and its contribution to development of reservoir porosity and permeability in the Kela 2 gas field,Tarim Basin,China

This study is undertaken to understand how calcite precipitation and dissolution contributes to depth-related changes in porosity and permeability of gas-bearing sandstone reservoirs in the Kela 2 gas field of the Tarim Basin, Northwestern China. Sandstone samples and pore water samples are col-lected from well KL201 in the Tarim Basin. Vertical profiles of porosity, permeability, pore water chem-istry, and the relative volume abundance of calcite/dolomite are constructed from 3600 to 4000 m below the ground surface within major oil and gas reservoir rocks. Porosity and permeability values are in-versely correlated with the calcite abundance, indicating that calcite dissolution and precipitation may be controlling porosity and permeability of the reservoir rocks. Pore water chemistry exhibits a sys-tematic variation from the Na2SO4 type at the shallow depth (3600-3630 m), to the NaHCO3 type at the intermediate depth (3630―3695 m),and to the CaCl2 type at the greater depth (3728―3938 m). The geochemical factors that control the calcite solubility include pH, temperature, pressure, Ca2 concen-tration, the total inorganic carbon concentration (ΣCO2), and the type of pore water. Thermodynamic phase equilibrium and mass conservation laws are applied to calculate the calcite saturation state as a function of a few key parameters. The model calculation illustrates that the calcite solubility is strongly dependent on the chemical composition of pore water, mainly the concentration difference between the total dissolved inorganic carbon and dissolved calcium concentration (i.e., [ΣCO2] -[Ca2 ]). In the Na2SO4 water at the shallow depth, this index is close to 0, pore water is near the calcite solubility. Calcite does not dissolve or precipitate in significant quantities. In the NaHCO3 water at the intermedi-ate depth, this index is greater than 0, and pore water is supersaturated with respect to calcite. Massive calcite precipitation was observed at this depth interval and this intensive cementation is responsible for decreased porosity and permeability. In the CaCl2 water at the greater depth, pore water is un-der-saturated with respect to calcite, resulting in dissolution of calcite cements, as consistent with microscopic dissolution features of the samples from this depth interval. Calcite dissolution results in formation of high secondary porosity and permeability, and is responsible for the superior quality of the reservoir rocks at this depth interval. These results illustrate the importance of pore water chemis-try in controlling carbonate precipitation/dissolution, which in turn controls porosity and permeability of oil and gas reservoir rocks in major sedimentary basins.     

2003年7月4~5日梅雨锋暴雨维持的诊断分析

利用卫星云图、 多普勒雷达产品以及探空资料, 结合NCEP/NCAR再分析资料, 对2003年7月4~5日淮河流域大暴雨过程发生的环境场条件、 强降水的中尺度特征、 低空急流与能量锋的配置对强降水天气的影响等进行了详细的天气学分析, 并对大气正压非平衡强迫、 低空急流与能量锋相互作用对强降水天气发生\, 发展与持续过程中的影响进行了动力诊断。结果表明： 这次梅雨锋暴雨过程, 暴雨区上空气柱内水汽较少, 孟加拉湾与南海地区向暴雨区输送的水汽占据主导地位。暴雨区的平均散度与垂直速度变化与强降水天气变化比较一致。对流层低层能量锋与低空急流的配置及其相互作用对强降水天气的发生\, 发展和维持具有重要影响。当低层能量锋与低空急流处于同时强的配置状态时, 强降水天气发生并持续; 当两者处于一强一弱或两者皆弱的配置状态时, 则没有强降水天气发生或持续。正压非平衡强迫对强降水启动作用较大, 而湿斜压热动力相互作用对强降水天气持续影响较大, 是导致强降水过程维持的主要动力机制。     

Prograde pressure–temperature paths in the pelitic schists of the Sambagawa metamorphic belt, SW Japan

Prograde P–T paths recorded by the chemistry of minerals of subduction‐related metamorphic rocks allow inference of tectonic processes at convergent margins. This paper elucidates the changing P–T conditions during garnet growth in pelitic schists of the Sambagawa metamorphic belt, which is a subduction related metamorphic belt in the south‐western part of Japan. Three types of chemical zoning patterns were observed in garnet: Ca‐rich normal zoning, Ca‐poor normal zoning and intrasectoral zoning. Petrological studies indicate that normally‐zoned garnet grains grew keeping surface chemical equilibrium with the matrix, in the stable mineral assemblage of garnet + muscovite + chlorite + plagioclase + paragonite + epidote + quartz ± biotite. Pressure and temperature histories were inversely calculated from the normally‐zoned garnet in this assemblage, applying the differential thermodynamic method (Gibbs' method) with the latest available thermodynamic data set for minerals. The deduced P–T paths indicate slight increase of temperature with increasing pressure throughout garnet growth, having an average dP/dT of 0.4–0.5 GPa/100 °C. Garnet started growing at around 470 °C and 0.6 GPa to achieve the thermal and baric peak condition near the rim (520 °C, 0.9 GPa). The high‐temperature condition at relatively low pressure (for subduction related metamorphism) suggests that heating occurred before or simultaneously with subduction.