THERIA_G: a software program to numerically model prograde garnet growth

We present the software program THERIA_G, which allows for numerical simulation of garnet growth in a given volume of rock along any pressure–temperature–time (P–T–t) path. THERIA_G assumes thermodynamic equilibrium between the garnet rim and the rock matrix during growth and accounts for component fractionation associated with garnet formation as well as for intracrystalline diffusion within garnet. In addition, THERIA_G keeps track of changes in the equilibrium phase relations, which occur during garnet growth along the specified P–T–t trajectory. This is accomplished by the combination of two major modules: a Gibbs free energy minimization routine is used to calculate equilibrium phase relations including the volume and composition of successive garnet growth increments as P and T and the effective bulk rock composition change. With the second module intragranular multi-component diffusion is modelled for spherical garnet geometry. THERIA_G allows to simulate the formation of an entire garnet population, the nucleation and growth history of which is specified via the garnet crystal size frequency distribution. Garnet growth simulations with THERIA_G produce compositional profiles for the garnet porphyroblasts of each size class of a population and full information on equilibrium phase assemblages for any point along the specified P–T–t trajectory. The results of garnet growth simulation can be used to infer the P–T–t path of metamorphism from the chemical zoning of garnet porphyroblasts. With a hypothetical example of garnet growth in a pelitic rock we demonstrate that it is essential for the interpretation of the chemical zoning of garnet to account for the combined effects of the thermodynamic conditions of garnet growth, the nucleation history and intracrystalline diffusion. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.

全球海洋与大气界面的熵通量估算

给出并讨论了海洋系统中由于热量交换、物质交换以及外力做功引起的熵通量的表达式;同时,根据新近调整的全球海 气界面的气候平均资料,估计了全球海洋与大气界面气候年平均的熵通量(熵流),这一熵通量主要取决于海 气界面的热量和物质交换的空间不均匀性。计算结果显示,由热量交换分量引起的熵通量对海洋系统的总熵通量起到主要的贡献作用,其值约为-555.6mW·(m2·K)-1;由海表风应力做功引起的熵通量相对较小,约为-0.09mW·(m2·K)-1;由物质交换引起的熵通量最小,仅为-0.02mW·(m2·K)-1。总的来说,海洋系统从外界获得的总熵通量为-555.7mW·(m2·K)-1,这也就意味着在气候平均定态下,海洋系统内部的熵产生在量值上等于系统的熵交换,即为555.7mW·(m2·K)-1。海洋系统的负熵流与其内部的各种不可逆过程引起的熵产生取得平衡,确保了全球海洋系统处于非平衡热力学定态,并维持着海洋系统中各种尺度的时 空有序现象的消长过程。     

低温分解钾长石的热力学研究

通过不同温度、浓度、分压下ΔrGm的计算和不同条件下对平衡常数K的影响,作出ΔrGm～—T、ΔrGm—C、ΔrGm—P图,把热力学的一些规律应用于钾长石低温分解中,对参与低温分解钾长石的各物质能量转换进行分析判断反应进行的方向和限度,对钾长石的分解有指导作用。从热力学角度分析,在低温条件下分解钾长石的反应是可能的。     

Application of Linear Thermodynamics to the Atmospheric System. Part Ⅰ: Linear Phenomenological Relations and Thermodynamic Property of the Atmospheric System

从一般的热力学原理或其它自然原理对唯象关系所强加的限制，能够演绎出大气系统的一系列热力学性质。利用非平衡态线性热力学导出了湍流K闭合理论中湍流交换系数同唯象系数的关系，从理论上证明大气系统热量湍流输送同水泡之间存在交叉耦合，还导出了湍流强度同速度和位温梯度的关系，从而证明速度和位温空间分布的非均匀性是湍流之源。并证明湍流强度定理，不可压缩气体和各向同性湍流大气中，湍流强度正比于速度与位温梯度的标积。进而证明大气涡旋定理，位温的切变将导致涡旋运动或各种环流运动，速度涡度等于速度同位温相对梯度的矢积。展现了线性热力学在大气系统的应用前景。     

固溶体矿物的性质对计算河南西峡红柱石矿形成条件的影响

自然界的大多数造岩矿的是由两种或多种组分混合而成的固溶体。因此，在矿物，岩石和矿床等地质体的平衡热力学研究中不可避免地要涉及固溶体矿物热力学地为的问题。河南省西峡县杨乃沟红柱石矿泥质片岩中仅出现红柱石而没有蓝晶石和夕线石，红柱石矿物包裹体测温结果为420－600℃。通过矿物共生平衡p-t曲线所计算出的片岩形成温度和压力条件也应位于上述岩石学和岩相学等特征所限定的范围内。以此为基础，通过构筑矿物共生p-t平衡曲线的方法，对片岩中若干固溶体矿物理想性／非理想性问题进行了研究。其中斜长石必须以非理想固溶体处理，而石榴子石，黑云母和白云母视作理想固溶体的计算结果同片岩的岩石学和岩相学等特征相一致。     

高温高压下电解质溶液热力学性质的研究进展

高温高压下电解质溶液热力学性质的研究不仅对探讨地球内部流体的作用具有重要意义，而且在很多实际工业过程中也都有广泛应用。本综述了近10年来高温高压下电解质溶液热力学参数的实验测量和理论计算的进展，实验设备还有待进一步的改进和完善，以获得更高温度和压力下的数据，理论计算不仅有待于实验的发展，也与溶液的结构理论密切相关。     

An automated strategy for calculation of phase diagram sections and retrieval of rock properties as a function of physical conditions

We formulate an algorithm for the calculation of stable phase relations of a system with constrained bulk composition as a function of its environmental variables. The basis of this algorithm is the approximate representation of the free energy composition surfaces of solution phases by inscribed polyhedra. This representation leads to discretization of high variance phase fields into a continuous mesh of smaller polygonal fields within which the composition and physical properties of the phases are uniquely determined. The resulting phase diagram sections are useful for understanding the phase relations of complex metamorphic systems and for applications in which it is necessary to establish the variations in rock properties such as density, seismic velocities and volatile‐content through a metamorphic cycle. The algorithm has been implemented within a computer program that is general with respect to both the choice of variables and the number of components and phases possible in a system, and is independent of the structure of the equations of state used to describe the phases of the system.     

In situ methods for studying adsorbed phases at the solid/liquid interface: microcalorimetry and ellipsometryLes méthodes d'étude in situ des phases adsorbées : microcalorimétrie et ellipsométrie

The applications of calorimetric and ellipsometric methods to the understanding of adsorption phenomena occurring at the solid–liquid interface are presented with examples in the field of surfactant adsorption. The various experimental approaches are presented and compared, i.e., immersion calorimetry, titration calorimetry and liquid flow calorimetry. It is shown how they can be used to follow, in situ, the building steps of the surfactant adsorbed layer. On the other hand, ellipsometry allows the adsorption isotherm, the adsorption kinetics as well as the thickness of the adsorbed layer to be determined on well-defined flat surfaces. To cite this article: R. Denoyel, C. R. Geoscience 334 (2002) 689–702.     

流体的热力学前缘研究

总结了当前国内外关于流体的热力学前缘研究领域如下：（１）流体体系的ｐ－Ｖ－Ｔ－ｘ相关系研究，主要对象是Ｈ２Ｏ－ＣＯ２－盐类多组分体系高温高压下相图的实验和理论研究。（２）矿物在流体中的溶解度及溶解后在流体中溶解类型的形式和热力学性质——平衡常数（或Ｇｉｂｂｓ自由能）及各种偏摩尔性质的研究。（３）流体热力学模型化研究，已研制出大量的计算机软件，包括多种矿物、溶解类型的热力学数据库和模拟热液平衡、矿物溶解性质、反应路径和水—岩相互作用的实用程序。（４）超临界流体的相关系和化学反应等有许多特殊的性质，对认识地球内部的演化将有重要意义。（５）新技术新方法的发展，使分析单个矿物包裹体成分变成了现实。     

地洼盆地砂岩铜矿床成矿作用的化学动力学和热力学研究

对我国南方中新生代地洼盆地中的砂岩铜矿床进行了化学动力学与热力学的理论与实验研究。矿源岩中以辉铜矿和黄铜矿最有利于溶解和迁移，ＮａＣｌ对Ｃｕ的溶解和含矿流体的形成起了催化作用。溶液中Ｃｕ以络合物的形式迁移，其中以一价铜氯络合物为主；温度的降低和溶液中性化导致了络合物的失稳、分解和铜矿物的沉淀。铜矿物的化学动力学和热力学制约了砂岩铜矿中以辉铜矿为主及矿床分带的形成。