Interfacial energy effects and the evolution of pore size distributions during quartz precipitation in sandstone

Pore size is usually thought to control the rate of crystal growth in porous geological media by determining the ratio of mineral surface area to fluid volume. However, theory suggests that in micron-scale to nanometer scale pores, interfacial energy (surface energy) effects can also become important. Interfacial energy typically increases the solubility of very small crystals growing in tiny pores, and when the fluid is close to equilibrium - as is often the case in geological systems - mineral precipitation could occur in relatively large pores, while in very small adjacent pores crystal growth might be suppressed. Such a mechanism would effectively restrict the reactive surface area of the porous medium, thereby reducing the bulk reaction rate. We investigated the pore size distributions in naturally cemented sandstone adjacent to an isolated stylolite and found that quartz precipitation was inhibited in pores smaller than 10 μm in diameter. Furthermore, we demonstrate that kinetic formulations which assume constant solubility cannot reproduce the observed pore size patterns in mineralized samples; by contrast, excellent fits with the data are obtained when interfacial energy effects are taken into account. Reaction rates in geological media determined in field studies can be orders of magnitude lower than those measured in laboratory experiments, and we propose that reduced reaction rates in porous media with micron and submicron-scale porosity could account for much of the apparent paradox.     

单程波法地震波衰减特征数值模拟分析

在非均匀粘弹性介质中,地震波衰减研究能够有效揭示地层吸收特性对地震波的影响。这里从单程波方程出发,结合粘弹性介质中的复波数理论,考虑介质的横向变化,采用分步傅立叶波场延拓技术,推导出适用于横向变速介质的带Q地震记录计算公式,最后将此方法应用于四个不同含Q地层模型。试验表明：单程波法计算速度快,波场信息简单清晰,易于深入分析和反演算法的建立。并且,Q值对地震波波形、能量、频率等都产生了较为明显的影响,对实际资料能量补偿、地震资料分辨率的提高,以及利用衰减特征进行储层识别有一定指导价值。     

Role of hydrogen in the formation of associated gases and postsedimentation transformations of salt rocks of the Verkhnekamskoe deposit

In this paper we discuss relationships between the intensity of epigenetic transformations and the distribution of organic matter, calcium sulfates, and hydrogen in a salt sequence. The timing of incipient epigenetic transformations in the rocks of a potassic salt bed coinciding with the beginning of the radiolysis of crystallization water in carnallite was established. The role of hydrogen in the formation of associated gases and postsedimentation transformations of the salt rocks of the Verkhnekamskoe deposit was evaluated. The formation of methane and associated gases was attributed to the influence of molecular hydrogen on organic matter and sulfur minerals during sulfate reduction.     

新疆乌拉泊水均衡试验场凝结水对地下水补给的观测研究

通过1989~1995年新疆乌拉泊水均衡试验场潜水埋深4m处包气带凝结水对地下水补给的观测:卵砾石2.58mm/a、细砾3.15mm/a、中砂9.90mm/a、细砂35..87mm/a、粉土10.04mm/a。最有利于包气带凝结水形成的时间是每年的4~9月;包气带凝结水量的大小与土体颗粒相对比表面积和渗透系数相关,推测粉砂的凝结水量约为20mm/a,粘性土小于10mm/a;凝结水对地下水补给的最大量约为50mm/a。综合气候和水文地质条件分析,认为本试验研究成果在我国西北干旱区具有代表性,估算西北地区凝结水对地下水的总补给量大于3×1010m3/a,可能大于平原降水入渗量,在某些区域可能是最主要的地下水补给源。     

九台营城煤矿区珍珠岩特征、成因及储层地质意义

九台营城煤矿区珍珠岩类型多样、种类繁多：按珍珠岩成分和组构可分为强蚀变珍珠岩、流纹构造珍珠岩、流纹构造与珍珠构造互层珍珠岩、含斑晶珍珠岩和硅化珍珠岩;根据珍珠岩蚀变阶段和蚀变产物又可分为未蚀变（正常）珍珠岩、弱蒙脱石化珍珠岩、强蒙脱石化珍珠岩和硅化-蒙脱石化珍珠岩。本区珍珠岩为熔岩喷出地表后,直接进入水中,发生塑状玻璃的水化作用冷凝固结形成。其蚀变过程是在碱性水介质参与下完成的。本区珍珠岩具有随蚀变程度加强而储集性能大大降低的特征。     

黄陵矿区富油煤对流加热原位转化开发效果数值模拟

有效开发富油煤提取石油对缓解我国油气紧张具有重要的现实意义,地下原位开采对流加热技术是富油煤有效开发的主要技术之一。以黄陵矿区延安组富油煤层为例,将高温蒸汽和氮气作为加热介质,采用地下原位转化开采对流加热的技术手段,分别研究2种加热介质在不同注入压力下的开采效果与能量回报率。结果表明：当注入气体的温度为400℃时,注蒸汽开采的加热效率更高,相同注入压力下注蒸汽开采将地层干酪根开采完所需要的时间小于注入高温氮气,二者比例为0.52～0.68,节省时间效果明显,注蒸汽开采与注氮气开采的天然气总产量比例为1.07～1.11,油总产量比例为0.82～0.85,二者差值随注入压力的增加而逐渐减小。注蒸汽开采与注氮气开采的能量回报率比例为1.754～2.363,注蒸汽开采注入压力为6 MPa时能量回报率在4.99 a达到峰值1.796,注氮气开采均未达到能量正收益。无论哪种加热介质,增加注入压力都能够缩短加热反应时间,有利于提高注蒸汽能量回报率。注氮气开采的地层流体有效渗透率较高,利于油气在地层中流动。注蒸汽开采在富油煤清洁开采方面具有优越性,为富油煤清洁开采的具体生产过程提供一定的数据参考依据。     

基于烃类垂向微渗漏的地球化学场数值模拟

基于烃类微渗漏基本理论和连续介质假设,总结了近年来地球化学勘探领域主流的关于烃类微渗漏机制的假说;根据其中最为普遍接受的烃类气体以胶体大小的微气泡做布朗运动向上运移为主的微渗漏机制,利用多孔介质流体动力学以及能量守恒定律建立了定量描述烃类微渗漏的数学模型;采用构建单层和多层积木块理想地层介质模型叠加的方法对典型地质条件进行了划分和组合;建立了描述地层介质模型内部烃类垂向微渗漏过程的定量方程,即一类反应-对流-扩散偏微分方程,进行了“油气藏中烃类组分垂向微渗漏和异常形成动态过程”的数学描述和模拟,并将上述过程付诸于典型实践区--鄂尔多斯盆地花豹沟油气藏进行模型的数值验证与实例分析,得到与实际勘探数据相一致的结果。研究成果为复杂条件下油气运移定量地球化学场数学模型的建立提供了一种新的思想和具体数学方法。     

The fluid regime of crystallization of water-saturated granitic and pegmatitic magmas: a physicochemical analysis

Miarolitic granite pegmatites are a unique natural object that makes it possible to study magmatic processes that lead to the formation of ore-forming media and systems. This paper summarizes modern views on phase transformations in aqueous silicate systems at parameters close to those of the transition from magmatic to hydrothermal crystallization. Comparison of phase diagrams and the results of study of pegmatite-forming media permits making conclusions about the crystallization of the water-saturated magmas of miarolitic granite pegmatites. The fluid regime of aqueous granite systems of simple composition, not enriched in fluxing components, is determined mainly by magma degassing or the supply of volatiles with flows of transmagmatic fluids. These processes cause the separation of essentially carbon dioxide or essentially hydrous fluid. During the evolution of such magmas, crystallization from silicate melt is separated in PT-space and, possibly, in time from the crystallization from aqueous or mixed carbon dioxide-aqueous super- and subcritical solutions. The evolution of chambers of water-saturated granitic and pegmatitic magma enriched in F, B, and alkali metals presupposes the formation of a heterogeneous mineral-forming medium in which crystallization occurs in the magmatic melt at high-temperature stages; as temperature decreases, crystallization can proceed in hydrous fluid, hydrosilicate, and/or hydrosaline liquids simultaneously. Hydrothermal crystallization can also take place in a heterogeneous medium consisting of aqueous solutions of different salinities and vapor or vapor-carbon dioxide gas mixture. The relationship between different fluid regimes during the evolution of volatile-saturated granitic and pegmatitic magmas determines the variety of postmagmatic rocks accompanying granite massifs.     

Experiments on phase transformations and chemical reactions of mechanically activated minerals by grinding: Petrogenetic implications

Prolonged grinding increases the energy of solids by the production of stored energy in the form of new surfaces and internal defects. Moreover, grinding also generates quasi-hydrostatic pressures which can result in polymorphic transformations and mineral decomposition. Here we demonstrate the solid-state transformation of metastable to stable polymorphs (aragonite → calcite, anatase → rutile); the transformation of low-pressure to high-pressure phases (calcite → aragonite); and the lowering of the dehydration and decarbonation temperatures of minerals (siderite → magnetite or hematite, diaspore → corundum).In the presence of a fluid phase, stored energy from grinding can be released, resulting in accelerated reaction rates and, more importantly, phase transformations. In this paper we demonstrate the following transformations: ground calcite → magnesian calcite (at low Mg²⁺ concentration in solution), ground calcite → aragonite (at high Mg²⁺ concentration), ground magnesite → hydromagnesite, and ground dolomite → aragonite + Mg²⁺.Assuming an analogy between laboratory and natural grinding, tectonic activity may have important consequences on the release of hydrothermal fluids, the solubilization of minerals and on solid-state transformations. As examples the possible role of deformation on the formation of metamorphic aragonite and diaspore-bauxites is discussed.     

Dehydroxylation mechanisms in Al/Fe dioctahedral phyllosilicates by quantum mechanical methods with cluster models

Atomic models involving the dehydroxylation process of dioctahedral phyllosilicates without interlayer charge were used to calculate energies and explore the reaction paths of the possible mechanisms of this reaction at a quantum mechanical level. The geometrical features and electronic structure of a molecular cluster model of two edge-sharing octahedrally coordinated cations coupled to a ring of six silicate tetrahedra was evaluated by ab initio molecular orbital calculations with Hartree-Fock approximation. Two dehydroxylation mechanisms are considered. One mechanism involves two contiguous hydroxyl that are on an octahedron shared edge that joins a pair of octahedral cations. The other model considered involves OH loss from across an octahedral vacant. The substitution effect of Al³⁺ by Fe³⁺ in the octahedral sheet on the activation energy and structural transformations is compared by minimization of the critical points of the Potential Energy Surface (PES) for the reactant, transition state and product along the reaction path of the dehydroxylation process. The calculated energy differences and vibration frequencies are according to previous experimental results. The dehydroxylation mechanism involving OH across the octahedral hole, is less energetically favorable and is endothermic.     

Matlab环境下瑞利波有限差分正演与曲线绘制

以瑞利波频散方程为出发点的Abo-Zena传递矩阵等方法,只能研究层状介质中瑞利波的传播特性,对于非层状介质,传递矩阵无能为力。因此,不得不考虑有限元、有限差分等方法。根据弹性动力学方程,采用交错网格有限差分方法对均匀弹性半空间介质进行全波场模拟,并在Matlab环境下实现编程计算,再现了瑞利波在近地表的传播状态,实现了地震剖面曲线的正振幅充填问题,从而获得了类似野外地震勘探的剖面记录。模拟结果表明,采用一阶差分格式所得到的地震记录存在较严重的数值频散,在采用有限差分法研究瑞利波"之"字形成因时,须尽量压制数值频散现象,才能获得更接近实际情况的频散曲线。      

二维随机介质对声波传播影响

地层的形成是随机性和不确定性,用基于随机理论的方法来描述更为适合。利用随机介质建模的方法来描述地下介质中的小尺度非均匀性。为了考察小尺度非均匀性介质中声波的传播特性,建立了不同尺度的二维随机介质模型,利用有限差分法模拟随机介质中的声波场。分别对比不同自相关长度条件下地震记录及其波形与振幅谱,研究这些特征量与随机介质模型的自相关长度的关系。结果表明,自相关长度作为描述小尺度非均匀性尺度的参量,对声波在随机介质中传播影响很大。     

Nanotechnology,global development in the frame of environmental risk forecasting. A necessity of interdisciplinary researches

Interdisciplinarity is of first importance to evaluate the risks associated with nanotechnology. The reasons are that nanomaterials are very new materials that combine nano-sizes and new reactivities. The complexity comes from the very low concentrations of nanomaterials in the environmental medium, the transformations of the nanomaterials due to the reactivity of the surface, the transfer in the environmental media, particularly in the presence of liquid water (soils, sediments, surface water), which implies an association with natural colloids (organic or minerals) and blockage in some compartments. These properties govern the hazard that strongly depends on exposure and speciation.     

Impact of the desorption energy of atomic oxygen on the chemical evolution in star-forming regions

The impact of a recently measured values of the desorption energy of oxygen released from the surface of silicate dust particles on the results of numerical simulations is analyzed. The chemical evolution of the interstellar medium under conditions corresponding to those in a cold, dark cloud is considered, together with the collapse of a translucent cloud into a dark cloud. Astrochemical modeling methods are used to show that, overall, there were no substantial changes in the chemical evolution under the conditions for the selected models for these objects, but the formation of somemolecules is sensitive to the change from the traditionally adopted oxygen desorption energy (800 K) to the new value (1850 K). The characteristics of the formation of such molecules are analyzed.     

Formation of galactic shocks and the vertical structure of the gaseous disk of the galaxy in a “turbulent” interstellar medium

The effects on the formation of Galactic shocks and the vertical structure of the Galactic disk due to thermal processes in a cloudy interstellar medium as it flows through a spiral density wave in the plane of the Galactic disk are considered. The evolution of the gas is fundamentally different, depending on the thermal properties of the medium. For example, if it is compressed in the horizontal direction (parallel to the Galactic plane) by the gravitational forces of the spiral density waves responsible for the formation of spiral arms, an isothermal and adiabatic medium is swept out in the vertical direction. However, on the contrary, a medium whose volume loss function increases fairly rapidly with density and temperature is further compressed under the action of the overall gravitational field of the galaxy. This effect is referred to as “self-focusing,” and may serve as an additional mechanism to explain the recently discovered anticorrelation between the width of the atomic hydrogen layer in the Galaxy and the gas density. The difference in the vertical behavior of media with different thermal properties can be used as an indicator of the thermal properties of a particular component of the interstellar gas (atomic or molecular). Attention is drawn to the fact that Galactic shocks themselves represent a mechanism that can heat the ensemble of clouds, i.e., increase the dispersion of cloud velocities. The vertical structure of a Galactic shock front is constructed, which is in qualitative agreement with the “bow shock” inferred from radio data.     

孔隙介质中天然气水合物相变过程的影响因素研究进展

天然气水合物储量巨大且富含甲烷,被视为21世纪最重要的潜在新型清洁能源之一.天然气水合物大多赋存在海底沉积物的孔隙介质中(少部分赋存于永久冻土层中),对其相变过程受孔隙介质影响规律的系统梳理和总结对未来的勘探开发具有重要意义.本文综合分析前人研究成果,将孔隙介质中天然气水合物的相变过程概化为水合物形成分解时的温压平衡条...     

碳酸钙颗粒的细菌诱导形成

为研究胶质芽孢杆菌（Bacillus mucilaginosus）在特定条件下能否诱导合成碳酸钙,作者采用胶质芽孢杆菌两种常用 基本培养基（有氮培养基和无氮培养基）,以磷灰石矿物为钙源,进行了利用胶质芽孢杆菌促进碳酸钙形成的实验,借助扫 描电镜（SEM）、能谱定量分析（EDS）和X-射线衍射（XRD）等手段观察分析形成碳酸钙的晶体结构和化学组成。结果表 明,胶质芽孢杆菌能促进碳酸钙晶体的形成,在有氮加磷矿粉的细菌培养液中形成的碳酸钙多于无氮加磷矿粉的细菌培养 液,在有氮加磷矿粉的细菌培养液中观察到柱状碳酸钙的形成。作者认为,胶质芽孢杆菌通过其风化作用及较强的吸附功能, 利用其分泌的碳酸酐酶（CA）和溶解CO2在分解磷灰石的过程中促进了碳酸钙的形成。     

稠环芳烃和多环芳烃成因模拟

通过模拟实验发现:硫与β-胡萝卜素反应可以形成稠环芳烃,硫或氧与联苯反应可以形成多种多环芳烃。稠环芳烃主要是以一个合适的分子为基础发展形成的,多环芳烃也可以由一个分子转化形成,但主要是两个或两个以上联苯等化合物分子连接起来而成。     

珊瑚砂三维孔隙微观特性研究

孔隙是多孔介质内渗流的发生场所,与介质渗透性存在必然的联系。珊瑚砂因其特殊的物质来源和形成过程,较陆源砂具有截然不同的孔隙特性。通过一系列微观研究手段,从本质上揭示了珊瑚砂特殊孔隙性质的原因。研究发现,从孔隙形状、孔喉尺寸和整体连通性3个角度描述孔隙性质较为合理。其中,孔隙形状用形状因子度量,孔喉尺寸包括孔隙半径和喉道半径,珊瑚砂多孔介质整体连通性利用配位数进行描述。而影响孔隙形状、孔喉尺寸和整体连通性的主导因素包括颗粒形状和颗粒表面粗糙度两方面。其中颗粒形状主要影响孔隙形状、喉道尺寸、孔喉尺寸离散性和介质内部连通性的均匀分布情况。颗粒表面粗糙度主要影响孔隙形状、孔隙形状离散性、孔隙尺寸和介质整体连通性。     

Similarities and differences in hydrous pyrolysis of biomass and source rocks

In laboratory simulation of oil generation, products from closed systems pyrolysis of immature source rocks in the presence of water gives the closest match to petroleum compositions observed in nature. Fresh biomass can also be converted to fluids by pyrolysis, but in the absence of the sedimentary diagenetic transformations, the initially much higher oxygen content gives high yields of oxygen containing products. In this work, the reactions that occur during hydrous pyrolysis of a Kimmeridge source rock, a brown coal and two polymeric waste materials from alginate production are compared in terms of quantities of the main products and kinetic models of the reaction systems. The biomass pyrolysis and the simulated maturation are described in similar reaction networks. Conversion of biomass to fluids occurred with reaction networks and activation energy distributions comparable to the brown coal, while for the Kimmeridge source rock reactions a simpler reaction network could be used. The biomass samples gave a high degree of conversion to fluid products, and higher yields of bitumen than the coal.