玄武岩地区水—岩作用的数值模拟

本文采用数值模拟方法,以热力学平衡原理为基础,定量研究地下水与岩石之间的化学反应变化过程,包括岩石中矿物的溶解、次生矿物沉淀以及水溶液中化学成分的变化,并对江苏省盱眙玄武岩地区进行了水－岩反应模拟分析,结果表明数值模拟计算具有较好的拟合效果。     

矿物-水反应的地球化学动力学研究进展

回顾了地球化学动力学这门新兴学科的产生与发展，评述了国内外矿物-水反应的地球化学动力学研究的新进展，介绍了矿物-水反应的溶解动力学及地球化学动力学模拟的新成果及应用领域。低温条件下硅酸盐和碳酸盐矿物与水的反应得到高度重视。硅酸盐矿物的溶解速率与溶液的pH值、离子强度、温度及有机酸的含量等密切相关。碳酸盐类矿物的溶解速率主要取决于温度、GO2分压、酸碱度及相关离子的活度等因素。氧化物、硫化物、及氟化物等的溶解沉淀的动力学研究开始得到关注。矿物-水反应的地球化学动力学模拟已成为一个很有前景的方向。     

中地壳的地球化学动力学和矿石成因

笔者重点进行了大于300℃——在近临界区至超临界区条件下的硅酸盐矿物与水反应动力学实验。矿物(钠长石Ab、透辉石Di、阳起石Act和磁铁矿Mt)的溶解反应动力学实验是使用流体通过叠层反应器的开放体系在25～400℃和22MPa下完成的。实验发现矿物在300℃至400℃范围,在跨越水临界点时出现反应速率的涨落。各种多金属氧化物硅酸盐与水反应时,各个元素溶解到溶液里的释放速率一般不一样,常称为一致溶解作用。但是,在近300℃变为一致溶解作用。实验发现在22MPa时硅酸盐矿物的最大溶解反应速率多是在300℃,如硅的最大释放速率是在300℃。其余元素如Na、K、Mg、Ca、Fe、Al等释放速率在<300℃22MPa时都高于硅的释放速率,在>300℃时硅的释放速率要高于其它元素的释放速率。确切地说,金属与氧之间的键的性质决定了它们(金属氧化物)与水之间反应速率。在一般情况下,Na-Obr,Ca-Obr,Mg-Obr,Al-Obr和Si-Obr的键桥(br),它们之间相对地由具有离子键性质逐步变为具有极性键的性质。由常温常压到亚临界区(300～374℃22MPa),再到大于临界点374℃、22MPa进入超临界区,水的性质随温度、压力变化。水由容易溶解离子键逐渐变为容易打破极性键。笔者还研究了黑钨矿、锡石(玄武岩、花岗闪长岩)与水在250～400℃条件下的反应动力学过程,得出了相同的结果。实验均发现在跨越水临界点时矿物(或岩石)与水反应的动力学涨落。这些实验结果可以用于说明中地壳上部的水/岩相互作用的特征。发生于中地壳的水、岩相互作用大多是在300～450℃和20～50MPa条件下进行的。各地区的地壳厚度不一,中地壳温度压力并不完全相同。模拟中地壳条件下水/岩相互作用实验,目的主要是研究矿物(或岩石)在300～450℃条件下反应动力学过程。已有热液矿床矿物流体包体数据表明:有一批矿床的主要矿石形成于300～500℃,低于NaCl H2O溶液临界线的条件。中地壳的流体处于由亚临界态跨越临界态,进入超临界流体太的演化过程。这种流体的性质变化会引起水/岩相互作用的反应动力学涨落和矿石大量沉淀。     

花岗岩—流体相互作用的实验研究进展

花岗岩－流体相互作用的实验研究，对于解决放射性腐废料的处理，地热能的有效开发利用和成岩成矿作用的理论研究等问题，具有重要的意义和应用价值。因此，本文引用近期的资料，从矿物表面的解吸作用，次生矿物的沉淀，矿物及花岗岩的溶解速率和花岗岩－流体反应的效应四信方面，对花岗岩－流体相互作用的实验研究进行论述，以期达到抛砖引玉的效果。     

含矿热液系统的化学动力学若干基本问题

作者进行开放-流动体系的矿物与水溶液反应动力学实验,研究流动环境,远离平衡状态的矿物溶解反应动力学过程。实验表明降温和降盐度的溶液内溶解反应减弱,并且流动条件有利于沉淀。从而说明一些矿床形成过程中的流动体系和化学动力学控制因素。同时,矿物与水溶液的流动反应动力学实验揭示大量非线性动力学现象。     

鄂尔多斯白垩系盆地地下水水-岩反应的锶同位素证据

利用鄂尔多斯白垩系盆地地下水锶同位素和水化学资料,对该区水-岩作用机制进行了分析,并采用反向水文地球化学模拟的方法对锶同位素示踪水-岩反应的分析结论进行了验证。结果表明:研究区主要发生了石膏、少量碳酸盐矿物及铝硅酸盐矿物的溶解反应,且北区地下水对石膏等硫酸盐矿物的溶滤作用强于南区,而南区地下水对铝硅酸盐矿物的溶滤作用强于北区;同时,南区碳酸盐矿物发生了溶解/沉淀的不一致性,即白云石发生溶解反应而方解石发生沉淀反应。采用锶同位素方法得出的水-岩作用结论与反向水文地球化学模拟结果相一致。     

烃源岩—流体相互作用模拟实验研究

为了探讨烃源岩与孔隙流体之间相互作用过程和机理以及有机酸的生成及其影响因素,我们开展了烃源岩-流体相互作用模拟实验研究。实验结果表明：Ⅱ型干酪根形成有机酸的能力大于Ⅰ型干酪根,水的矿化度对有机酸的形成影响甚微,随着温度升高,流体中有机酸的含量也随之增大。pH值对有机酸形成的影响非常明显,中性和碱性条件更有利于生成有机酸。其中乙酸的形成有利于碳酸盐矿物的溶解,而草酸的形成不利于碳酸盐的溶解。温度对烃源岩的影响与烃源岩的矿物组成有很大的关系,对于富碳酸盐烃源岩,Ca、Mg、Na三元素在水中的溶解量,与温度呈反相关的关系,对于贫碳酸盐烃源岩,与反应温度之间则呈现出正相关的关系。而无论碳酸盐含量高低,Si在溶液中的含量都会随着温度的升高而增大。酸性溶液对烃源岩的溶解能力最强,无论原始反应溶液的酸碱性,反应结果都最终趋于弱碱性。流体的含盐量对烃源岩中Mg的溶解影响差异较大,低盐度的流体有利于Mg溶解。     

烃源岩—流体相互作用模拟实验研究

为了探讨烃源岩与孔隙流体之间相互作用过程和机理以及有机酸的生成及其影响因素,我们开展了烃源岩-流体相互作用模拟实验研究。实验结果表明：Ⅱ型干酪根形成有机酸的能力大于Ⅰ型干酪根,水的矿化度对有机酸的形成影响甚微,随着温度升高,流体中有机酸的含量也随之增大。pH值对有机酸形成的影响非常明显,中性和碱性条件更有利于生成有机酸。其中乙酸的形成有利于碳酸盐矿物的溶解,而草酸的形成不利于碳酸盐的溶解。温度对烃源岩的影响与烃源岩的矿物组成有很大的关系,对于富碳酸盐烃源岩,Ca、Mg、Na三元素在水中的溶解量,与温度呈反相关的关系,对于贫碳酸盐烃源岩,与反应温度之间则呈现出正相关的关系。而无论碳酸盐含量高低,Si在溶液中的含量都会随着温度的升高而增大。酸性溶液对烃源岩的溶解能力最强,无论原始反应溶液的酸碱性,反应结果都最终趋于弱碱性。流体的含盐量对烃源岩中Mg的溶解影响差异较大,低盐度的流体有利于Mg溶解。     

地下水与玄武岩反应趋势分析

通过建立水化学平衡反应模型,计算地下水组分的各种可能存在形式的浓度和活度,并求得各种矿物饱和指数,再用饱和指数分析水－岩相互作用过程中矿物的溶解与沉淀反应趋势。本文采用该方法对盱眙玄武岩地区水－岩间反应趋势进行了分析。     

水-岩反应过程中的锂硼同位素分馏变化规律

作为热液体系中成矿的一个重要前提,水-岩反应一直以来都是矿床学的重要研究内容,亦是国际地学界的前沿问题。该过程伴随着同位素的交换,使流体和岩石的同位素组成发生变化。硼和锂同位素作为非传统的稳定同位素示踪工具,常用于限定流体和岩石的热液反应过程。本文对水-岩反应过程中影响硼和锂同位素分馏的因素作了较全面概述,包括温度、pH值、溶解过程、表面交换反应以及次生矿物的沉淀过程,并取得了一些主要认识:(1)一般地,低温或者高pH值时流体更快速富集11B并且在反应结束时有更高的δ11B值;低温(150℃)时锂进入次生矿物中,高温(200℃)时锂从岩石中萃取出来。(2)初始物质的溶解过程与表面交换反应对锂同位的分馏几乎没有影响。(3)一般而言,次生矿物的形成使7Li优先丢失进入溶液而富集重同位素。最后简单陈述了水-岩反应过程中硼和锂同位素组成的质量平衡模拟计算以及反映流体和岩石的同位素组成的变化。     

Coupled alkali feldspar dissolution and secondary mineral precipitation in batch systems – 2: New experiments with supercritical CO2 and implications for carbon sequestration

In order to evaluate the extent of CO₂–water–rock interactions in geological formations for C sequestration, three batch experiments were conducted on alkali feldspars–CO₂–brine interactions at 150–200 °C and 300 bars. The elevated temperatures were necessary to accelerate the reactions to facilitate attainable laboratory measurements. Temporal evolution of fluid chemistry was monitored by major element analysis of in situ fluid samples. SEM, TEM and XRD analysis of reaction products showed extensive dissolution features (etch pits, channels, kinks and steps) on feldspars and precipitation of secondary minerals (boehmite, kaolinite, muscovite and paragonite) on feldspar surfaces. Therefore, these experiments have generated both solution chemistry and secondary mineral identity. The experimental results show that partial equilibrium was not attained between secondary minerals and aqueous solutions for the feldspar hydrolysis batch systems. Evidence came from both solution chemistry (supersaturation of the secondary minerals during the entire experimental duration) and metastable co-existence of secondary minerals. The slow precipitation of secondary minerals results in a negative feedback in the dissolution–precipitation loop, reducing the overall feldspar dissolution rates by orders of magnitude. Furthermore, the experimental data indicate the form of rate laws greatly influence the steady state rates under which feldspar dissolution took place. Negligence of both the mitigating effects of secondary mineral precipitation and the sigmoidal shape of rate–ΔG_r relationship can overestimate the extent of feldspar dissolution during CO₂ storage. Finally, the literature on feldspar dissolution in CO₂-charged systems has been reviewed. The data available are insufficient and new experiments are urgently needed to establish a database on feldspar dissolution mechanism, rates and rate laws, as well as secondary mineral information at CO₂ storage conditions.     

Coupled alkali-feldspar dissolution and secondary mineral precipitation in batch systems: 1. New experiments at 200 °C and 300 bars

Batch reactor experiments were conducted to assess perthitic alkali-feldspar dissolution and secondary mineral formation in an initially acidic fluid (pH = 3.1) at 200 °C and 300 bars. Temporal evolution of fluid chemistry was monitored by major element analysis of in situ fluid samples. Solid reaction products were retrieved from two identical experiments terminated after 5 and 78 days. Scanning electron microscopy revealed dissolution features and significant secondary mineral coverage on feldspar surfaces. Boehmite and kaolinite were identified as secondary minerals by X-ray diffraction and transmission electron microscopy. X-ray photoelectron spectroscopy analysis of alkali-feldspar surfaces before and after reaction showed a trend of increasing Al/Si ratios and decreasing K/Al ratios with reaction progress, consistent with the formation of boehmite and kaolinite.Saturation indices of feldspars and secondary minerals suggest that albite dissolution occurred throughout the experiments, while K-feldspar exceeded saturation after 216 h of reaction. Reactions proceeded slowly and full equilibrium was not achieved, the relatively high temperature of the experiments notwithstanding. Thus, time series observations indicate continuous supersaturation with respect to boehmite and kaolinite, although the extent of this decreased with reaction progress as the driving force for albite dissolution decreased. The first experimental evidence of metastable co-existence of boehmite, kaolinite and alkali feldspar in the feldspar hydrolysis system is consistent with theoretical models of mineral dissolution/precipitation kinetics where the ratio of the secondary mineral precipitation rate constant to the rate constant of feldspar dissolution is well below unity. This has important implications for modeling the time-dependent evolution of feldspar dissolution and secondary mineral formation in natural systems.     

Estimation of reactive mineral surface area during water-rock interaction using fluid chemical data

Mineral dissolution and precipitation reactions actively participate to control fluid chemistry during water-rock interaction. However, it is difficult to estimate and normalize bulk reaction rates if the mineral surface area effectively participating in the reactions is unknown. In this study, we evaluated the changing of the reactive mineral surface area during the interaction between CO₂-rich fluids and albitite rock reacting under flow-through conditions. Our methodology, adopting an inverse modelling approach, is based on the measured chemical fluid composition as raw data. We estimated the rates of dissolution and the reactive surface areas of the different minerals by reconstructing the chemical evolution of the interacting fluids. This was done by a reaction process schema that was defined by a fractional degree of advance of the irreversible mass-transfer process and by attaining the continuum limit during the water-rock interaction. Calculations were carried out for albite, microcline, biotite and calcite assuming that the ion activity of dissolved silica and aluminium ions was limited by the equilibrium with quartz and kaolinite.We found that the absolute dissolution rate of albite, microcline, biotite and calcite remains essentially constant as a function of time, and the calcite dissolution rate is orders of magnitude higher than silicate minerals. On the contrary, the reactive surface area of the parent minerals varied by more than two orders of magnitude during the observed reaction time, especially for albite. We propose that the reactive surface area depends mainly on the stability of the secondary mineral coating that may passivate the effective reactive surface area of the parent minerals.     

Alkali feldspar dissolution and secondary mineral precipitation in batch systems: 3. Saturation states of product minerals and reaction paths

In order to evaluate the complex interplay between dissolution and precipitation reaction kinetics, we examined the hypothesis of partial equilibria between secondary mineral products and aqueous solutions in feldspar-water systems. Speciation and solubility geochemical modeling was used to compute the saturation indices (SI) for product minerals in batch feldspar dissolution experiments at elevated temperatures and pressures and to trace the reaction paths on activity-activity diagrams. The modeling results demonstrated: (1) the experimental aqueous solutions were supersaturated with respect to product minerals for almost the entire duration of the experiments; (2) the aqueous solution chemistry did not evolve along the phase boundaries but crossed the phase boundaries at oblique angles; and (3) the earlier precipitated product minerals did not dissolve but continued to precipitate even after the solution chemistry had evolved into the stability fields of minerals lower in the paragenesis sequence. These three lines of evidence signify that product mineral precipitation is a slow kinetic process and partial equilibria between aqueous solution and product minerals were not held. In contrast, the experimental evidences are consistent with the hypothesis of strong coupling of mineral dissolution/precipitation kinetics [e.g., Zhu C., Blum A. E. and Veblen D. R. (2004a) Feldspar dissolution rates and clay precipitation in the Navajo aquifer at Black Mesa, Arizona, USA. In Water-Rock Interaction (eds. R. B. Wanty and R. R. I. Seal). A.A. Balkema, Saratoga Springs, New York. pp. 895-899]. In all batch experiments examined, the time of congruent feldspar dissolution was short and supersaturation with respect to the product minerals was reached within a short period of time. The experimental system progressed from a dissolution driven regime to a precipitation limited regime in a short order. The results of this study suggest a complex feedback between dissolution and precipitation reaction kinetics, which needs to be considered in the interpretation of field based dissolution rates.     

构造-流体-成矿体系的反应-输运-力学耦合模型和动力学模拟

建立了一个综合的构造流体成矿体系的反应输运力学耦合动力学模型。利用有限元方法求解岩石变形、断裂作用和断裂网络统计动力学、流体流动、有机和无机地球化学反应及成岩成矿作用、压力溶液和其它压实力学、热迁移的方程组 ,可以对构造流体成矿体系的动力学演化过程进行 1～ 3维数值模拟。模拟的主要内容是在各种过程耦合作用下描述构造流体成矿体系的主要变量的时空演化 :( 1)与成矿流体的形成和性质有关的变量 ,如地层中矿物 (包括成矿物质 )的溶解速率、流体中各组分的浓度与饱和度、流体温度、压力、离子强度等 ;( 2 )与构造变形和流体运移有关的各变量 ,如应力与变形速率、岩石孔隙度、构造 (断裂 )渗透率等 ;( 3 )与沉淀成矿有关的变量 ,如矿物 (金属矿物和脉石矿物 )的成核速率、各矿物的沉淀量等 ;( 4 )上述各有关变量间的时空耦合关系 ,如断裂渗透率时空演化与流体流动、汇聚和成矿的耦合关系等。以湖南沃溪金锑钨矿床为例 ,应用该模型和方法对成矿动力学过程和动力学机制进行了初步的模拟与分析。     

Coupled alkali feldspar dissolution and secondary mineral precipitation in batch systems: 4. Numerical modeling of kinetic reaction paths

This paper explores how dissolution and precipitation reactions are coupled in batch reactor experimental systems at elevated temperatures. This is the fourth paper in our series of “Coupled Alkali Feldspar Dissolution and Secondary Mineral Precipitation in Batch Systems”. In our third paper, we demonstrated via speciation-solubility modeling that partial equilibrium between secondary minerals and aqueous solutions was not attained in feldspar hydrolysis batch reactors at 90-300 °C and that a strong coupling between dissolution and precipitation reactions follows as a consequence of the slower precipitation of secondary minerals (Zhu and Lu, 2009). Here, we develop this concept further by using numerical reaction path models to elucidate how the dissolution and precipitation reactions are coupled. Modeling results show that a quasi-steady state was reached. At the quasi-steady state, dissolution reactions proceeded at rates that are orders of magnitude slower than the rates measured at far from equilibrium. The quasi-steady state is determined by the relative rate constants, and strongly influenced by the function of Gibbs free energy of reaction (ΔG_r) in the rate laws.To explore the potential effects of fluid flow rates on the coupling of reactions, we extrapolate a batch system (Ganor et al., 2007) to open systems and simulated one-dimensional reactive mass transport for oligoclase dissolution and kaolinite precipitation in homogeneous porous media. Different steady states were achieved at different locations along the one-dimensional domain. The time-space distribution and saturation indices (SI) at the steady states were a function of flow rates for a given kinetic model. Regardless of the differences in SI, the ratio between oligoclase dissolution rates and kaolinite precipitation rates remained 1.626, as in the batch system case (Ganor et al., 2007). Therefore, our simulation results demonstrated coupling among dissolution, precipitation, and flow rates.Results reported in this communication lend support to our hypothesis that slow secondary mineral precipitation explains part of the well-known apparent discrepancy between lab measured and field estimated feldspar dissolution rates (Zhu et al., 2004). Here we show how the slow secondary mineral precipitation provides a regulator to explain why the systems are held close to equilibrium and show how the most often-quoted “near equilibrium” explanation for an apparent field-lab discrepancy can work quantitatively. The substantiated hypothesis now offers the promise of reconciling part of the apparent field-lab discrepancy.     

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。     

构造成矿非线性动力学:1.递增应力流变学模型

本文提出了构造成矿作用动力学研究的递增应力流变学方法。利用该方法将构造变形、应力、流体流动、地球化学反应及成岩成矿作用等多过程耦合起来，可以从多种地质过程的耦合与反馈作用对构造成矿的动力学演化过程进行１～３维数值模拟。模拟的主要内容是在各种过程耦合作用下，以下描述构造成矿体系的主要变量的时空演化：（１）与成矿流体的形成和性质有关的变量，如地层中矿物（包括成矿物质）的溶解速率、流体中各组分的浓度与饱和度、流体温度、压力、离子强度等；（２）与构造变形和流体运移有关的各变量，如应力与变形速率、岩石孔隙度、构造（断裂）渗透率等；（３）与沉淀成矿有关的变量，如矿物（金瞩矿物和脉石矿物）的成核速率、各矿物的沉淀量等；（４）上述各有关变量间的时空耦合关系，如断裂渗透率时空演化与流体流动、汇聚和成矿的耦合关系等。     

矿床地球化学应用

稳定同位素方法已成为现代地球科学研究的重要手段之一，稳定同位素体系的理论模式及其地球化学应用是国际上地球化学研究的前沿方向之一。本文概括了热液体系内成矿地球化学过程引起稳定同位素组成变化的定量理论模式，包括热液矿物之间的同位素平衡的判断、热液去气和矿物沉淀的储库效应、二元混合与矿床成因等。这些模型对于确定成矿温度、鉴定成矿流体源区和推测成矿地球化学机理提供了更为合理的同位素数据定量解释基础。     

Equilibrium-kinetic model of water-rock interaction

A computer model was developed for chemical interaction in water-rock systems. The model is based on the concept of partial equilibrium [1] and combines the calculation of chemical equilibria in multicomponent systems with accounting for the kinetics of the congruent dissolution of minerals as a function of pH (zeroth order kinetic reactions). The development of the process in time is simulated as a series of sequential partial equilibria, and the bulk chemical composition of the system is calculated at each time step from the chemical composition of aqueous solution at the beginning of the step and masses of minerals dissolved during time Δt. The dissolution rates of individual minerals are calculated at each time step for the given temperature, current pH value, and the degree of solution saturation with respect to minerals. Variations in the surface area of minerals due to precipitation and dissolution are accounted for. Model application is exemplified by the calculation of chemical equilibria in the water-granite system. The model may be useful for understanding the character of low-temperature interactions in water-rock systems under stagnant conditions, in particular, the multistage development of groundwater chemistry, interaction of liquid radioactive waste injected into underground repositories, etc.