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1.
It is generally accepted that the composition of ultrabasic nodules and their quantitative proportions do not significantly change during their transportation with kimberlitic magma to the Earth’s surface. We performed an experimental study of the relative stability of olivine, garnet, and pyroxenes in kimberlite melt at high pressure and temperatures (4 GPa, 1300–1500 °C). The study has shown that the loss in weight of minerals and, correspondingly, the rate of their dissolution in kimberlite melt differ considerably. The following sequence of the dissolution rates of minerals has been established: Cpx ≥ Opx > Gar > Ol. Pyroxenes are characterized by the most rapid dissolution, and olivine is the most stable mineral. The assumption is made that clinopyroxenites and websterites disintegrate more rapidly than dunites and lherzolites in kimberlitic magma.  相似文献   

2.
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–ΔGr 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.  相似文献   

3.
Hydrothermal alteration of a quartz‐K‐feldspar rock is simulated numerically by coupling fluid flow and chemical reactions. Introduction of CO2 gas generates an acidic fluid and produces secondary quartz, muscovite and/or pyrophyllite at constant temperature and pressure of 300°C and 200 MPa. The precipitation and/or dissolution of the secondary minerals is controlled by either mass‐action relations or rate laws. In our simulations the mass of the primary elements are conserved and the mass‐balance equations are solved sequentially using an implicit scheme in a finite‐element code. The pore‐fluid velocity is assumed to be constant. The change of rock volume due to the dissolution or precipitation of the minerals, which is directly related to their molar volume, is taken into account. Feedback into the rock porosity and the reaction rates is included in the model. The model produces zones of pyrophyllite quartz and muscovite due to the dissolution of K‐feldspar. Our model simulates, in a simplified way, the acid‐induced alteration assemblages observed in various guises in many significant mineral deposits. The particular aluminosilicate minerals produced in these experiments are associated with the gold deposits of the Witwatersrand Basin.  相似文献   

4.
This work presents new experimental results on surface chemistry of reacting minerals and interface kinetics between mineral and aqueous solutions. These experiments were carried out using a flow reactor (packed bed reactor) of an open system as well as a continuous stirred tank reactor, CSTR. The authors measured reaction rates of such minerals as zeolite, albite and carbonate (rhodochrosite, dolomite) in various solutions, and tested corresponding mineral surface by using SEM, XPS, SIMS, etc. This paper mainly presents the experimental results of zeolite dissolution in water and in low pH solutions at room temperature, and dolomite dissolution at elevated temperatures. The results show that the release rates of Si, Al and Na of zeolite are different in most cases. The incongruent dissolution of zeolite is related to surface chemical modifications. The Na, Al and Si release rates for dissolution of albite and zeolite in water and various solutions were measured as a function of temperature, flow veloci  相似文献   

5.
This publication provides a literature review on experimental studies of dissolution kinetics of mainly carbonates and feldspar group minerals, i.e. most common minerals at potential CO2-injection and/or storage sites. Geochemical interaction processes between injected CO2 and coexisting phases, namely reservoir and cap rock minerals and formation fluids close to the CO2-injection site can be simulated by flow-through or mixed flow reactors, while processes far from the injection site and long-term processes after termination actual CO2-injection can be mimicked by batch reactors. At sufficient small stirring rates or fluid flow rates as well as low solute concentrations flow-through reactors are also able to simulate processes far from the injection site. The experimental parameter temperature not only intensifies the dissolution process, the dominant dissolution mechanisms are also influenced by temperature. The dissolution mechanisms change from incongruent and surface controlled mechanisms at lower temperatures to congruent and transport controlled mechanisms at higher temperatures. The CO2 partial pressure has only a second order influence on dissolution behavior compared to the influence of pH-value and ionic strength of the CO2-bearing brine. Minerals exposed to CO2-bearing brines at elevated temperatures and pressures are subject of alteration, leading to severe changes of reactive surfaces and potential precipitation of secondary minerals.Computational simulations of mineral reactions at potential CO2 storage sites have therefore to include not only the time-resolved changes of dissolution behavior and hence kinetics of mineral dissolution, but also the influence of secondary minerals on the interaction of the minerals with CO2-enriched brines.  相似文献   

6.
The Cretaceous sandstone reservoir in the Kuche Depression, Tarim Basin, western China, was investigated with reference to its reservoir property evolution during diagenesis. Six general diagenetic stages were recognized through petrographic, mineralogical and geochemical analyses. Fluid–rock interaction experiments were conducted under these six continuous diagenetic conditions, that is with a simulation sequence of compaction → early diagenesis → organic acid incursion I → elevated temperature/pressure → organic acid incursion II → late diagenesis. Corresponding to these six experimental stages, a total of six models were constructed. Finally, an extended model of fluid–rock interaction during diagenesis at a geological timescale (from 30 Ma to present) was constructed after various parameters had been validated. Results demonstrate that the diagenetic stages from both the experimental and numerical simulations generally matched findings obtained from the petrographic and geochemical analyses: (i) With compaction becoming weakened, cementation by various minerals was gradually increased. (ii) Quartz overgrowth occurred because the contemporaneous sedimentary water was alkaline. (iii) Most minerals (for example, calcite and feldspar minerals) displayed dissolution owing to the first organic acid incursion, resulting in the visual porosity increasing to 29·26%. (iv) Increases in temperature and pressure caused a minor fluctuation of the porosity change. (v) The cement that formed during earlier stages largely dissolved with the second organic acid incursion. (vi) During the last stage, the reservoir fluid was diluted by sedimentary alkaline water and most minerals precipitated under an alkalic environment. The present porosity simulated is about 11·4%, comparable with the actually measured data. This study demonstrates that the combination of petrographic observations, laboratory experiments and numerical simulations can not only reconstruct the diagenetic process, but also provide a quantitative evaluation and prediction of reservoir petrophysical properties.  相似文献   

7.
The kinetics of dissolution of natural enargite in ammoniacal solution has been investigated. Unlike other copper sulfide minerals, the dissolution of copper from enargite is very slow and only 60% of the copper is extracted after 24 hours. The rate of dissolution is favored by high temperatures and high oxygen pressures. The experimental data seem to fit an electrochemical mechanism.  相似文献   

8.
雒斌 《地质与勘探》2019,55(1):223-230
鄂尔多斯盆地马岭地区为三角洲前缘沉积,长8_1油层属于低渗透、特低渗透、超低渗透致密砂岩油藏。综合铸体薄片、扫描电镜、物性等试验资料,深化认识马岭地区长8_1成岩作用特征;利用沉积环境、粘土矿物、古地温、R_o、流体包裹体温度等实验结论开展成岩阶段及成岩序列的研究;在成岩作用阶段中,压实和胶结-交代作用降低了部分孔隙度,溶蚀作用产出的次生孔隙是致密储层的高渗通道,在定性认识的同时设立储层孔隙度定量演化计算,实现了孔隙度演化的定量认识,且定量计算与气测孔隙度误差为3. 2%;通过研究4类样品表明,研究区长8_1属于强烈压实型成岩作用,不同成岩阶段孔隙的差异性直接导致了储层物性的好坏。  相似文献   

9.
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.  相似文献   

10.
The empirical rate laws formulated to describe the dissolution rates of oxide minerals include the surface charge concentration that results from the protonation and deprotonation of surface functional groups. Previous experiments on quartz and silica have shown that dissolution rates vary as a function of different background electrolyte solutions, however, such experiments are often conducted at elevated temperatures where it is difficult to estimate surface charge along with the dissolution rates. In the present study we measuresurface charge concentrations for silica in different electrolyte solutions at 298 K in order to quantify the extent to which the different counterions could affect the dissolution rates through their influence on the surface charge concentrations. The experimental solutions in the electrolyte series: LiCl, NaCl, KCl, RbCl, CaCl2, SrCl2 and BaCl2 were prepared to maintain a constant metal concentration of 1.0 M. For the alkali-metal chlorides, the surface charge concentrations correlate with the size of the hydrated alkali metal, consistent with the idea that these counterions affect charge via outer-sphere coordination that shield proton surface complexes from one another. The reactivity trend for alkaline-earth cations is less clear, but the data demonstrate distinct differences in the acid-base propertiesof the silica surface in these different electrolytes. We then discuss how these trends are manifested in the rate equations used to interpret dissolution experiments.  相似文献   

11.
This study presents lithium (Li) and magnesium (Mg) isotope data from experiments designed to assess the effects of dissolution of primary phases and the formation of secondary minerals during the weathering of basalt. Basalt glass and olivine dissolution experiments were performed in mixed through-flow reactors under controlled equilibrium conditions, at low pH (2-4) in order to keep solutions undersaturated (i.e. far-from equilibrium) and inhibit the formation of secondary minerals. Combined dissolution-precipitation experiments were performed at high pH (10 and 11) increasing the saturation state of the solutions (moving the system closer to equilibrium) and thereby promoting the formation of secondary minerals.At conditions far from equilibrium saturation state modelling and solution stoichiometry suggest that little secondary mineral formation has occurred. This is supported by the similarity of the dissolution rates of basalt glass and olivine obtained here compared to those of previous experiments. The δ7Li isotope composition of the experimental solution is indistinguishable from that of the initial basalt glass or olivine indicating that little fractionation has occurred. In contrast, the same experimental solutions have light Mg isotope compositions relative to the primary phases, and the solution becomes progressively lighter with time. In the absence of any evidence for secondary mineral formation the most likely explanation for these light Mg isotope compositions is that there has been preferential loss of light Mg during primary phase dissolution.For the experiments undertaken at close to equilibrium conditions the results of saturation state modelling and changes in solution chemistry suggest that secondary mineral formation has occurred. X-ray diffraction (XRD) measurements of the reacted mineral products from these experiments confirm that the principal secondary phase that has formed is chrysotile. Lithium isotope ratios of the experimental fluid become increasingly heavy with time, consistent with previous experimental work and natural data indicating that 6Li is preferentially incorporated into secondary minerals, leaving the solution enriched in 7Li. The behaviour of Mg isotopes is different from that anticipated or observed in natural systems. Similar to the far from equilibrium experiments initially light Mg is lost during olivine dissolution, but with time the δ26Mg value of the solution becomes increasingly heavy. This suggests either preferential loss of light, and then heavy Mg from olivine, or that the secondary phase preferentially incorporates light Mg from solution. Assuming that the secondary phase is chrysotile, a Mg-silicate, the sense of Mg fractionation is opposite to that previously associated with silicate soils and implies that the fractionation of Mg isotopes during silicate precipitation may be mineral specific. If secondary silicates do preferentially remove light Mg from solution then this could be a possible mechanism for the relatively heavy δ26Mg value of seawater. This study highlights the utility of experimental studies to quantify the effects of natural weathering reactions on the Li and Mg geochemical cycles.  相似文献   

12.
本文对辉铜矿、黄铜矿和斑铜矿在ＮａＣｌ溶液中的溶解动力学进行了实验研究，在２５－７０℃，溶解反应活化能分别为辉铜矿３６．４６ｋＪ／ｍｏｌ，黄铜矿４４．０５ｋＪ／ｍｏｌ，斑铜矿５１．９６ｋＪ／ｍｏｌ。最近探讨了动力学实验结果在砂岩铜矿成矿作用中的意义。  相似文献   

13.
A time-space continuum model for transport of hydrothermal fluids in porous media is presented which provides for simultaneous, reversible and irreversible chemical reactions involving liquids, gases and minerals. Homogeneous and heterogeneous reactions are incorporated in the model in a similar fashion through source/sink terms added to the continuity equation. The model provides for moving reaction fronts through surfaces of discontinuity across which occur jump discontinuities in the various field variables satisfying generalized Rankine-Hugoniot relations. Reversible reactions including aqueous complexing, oxidation-reduction reactions, mineral precipitation and dissolution reactions and adsorption are explicitly accounted for by imposing chemical equilibrium constraints in the form of mass action equations on the transport equations. This is facilitated by partitioning the reacting species into primary and secondary species corresponding to a particular representation of the stoichiometric reaction matrix referred to as the canonical representation. The transport equations for the primary species combined with homogeneous and heterogeneous equilibria result in a system of coupled, nonlinear algebraic/partial differential equations which completely describe the evolution of the system in time. Spatially separated phase assemblages are accommodated in the model by altering the set of independent variables across surfaces of discontinuity. Constitutive relations for the fluid flux corresponding to primary species are obtained describing transport of both neutral and charged species by advection, dispersion and diffusion. Numerical implementation of the transport equations is considered and both explicit and implicit finite difference algorithms are discussed. Analytical expressions for the change in porosity and permeability with time are obtained for an assemblage of minerals reacting reversibly with a hydrothermal fluid under quasi-steady state conditions. Fluid flow is described by Darcy's law employing a phenomenological expression relating permeability and porosity. Finally an expression for the local retardation factor of solute species is derived for the case of advective transport in a single spatial dimension which accounts for the effects of homogeneous and heterogeneous equilibria including adsorption on the rate of advance of a reaction front. The condition for the formation of shock waves is given.  相似文献   

14.
周自立 《沉积学报》1988,6(1):13-20
本文应用扫描电子显微镜及偏光显微镜,研究重矿物阶状石榴石表面的显微结构,确定它是自生成因的铁铝石榴石。根据阶状石榴石在各探井剖面中的纵向分布规律及特征变化,可以推断它的形成与埋藏深度或地温关系密切。通过计算确定,阶状石榴石初始形成的温度为92±5℃,可作为成岩矿物地温计。这对评价新探区的生油岩及储集岩均有实际意义。  相似文献   

15.
Borehole studies of the Soultz-sous-Forêts granite are dedicated to deep geothermics. The hydraulic properties of the reservoir are mainly controlled by the occurrence of some altered cataclastic shear zones showing a low natural permeability characterized by the occurrence of brines. Those zones show a fracture cluster organisation with sealed fractures of various types (post-filled joints, sheared fractures, veins). The main hydrothermal deposits observed within the permeable zones are geodic quartz, carbonates, illite and more locally sulphides. The fracture wall–rocks are intensely transformed: dissolution of igneous minerals, crystallization of new minerals, porosity and permeability increase. It is important to characterize the newly-formed minerals in order to choose the reagents used to improve the permeability of the exchanger by chemical stimulations. This article represents a synthesis of the studies completed by the authors between 1990 and 2008 on the fracture networks, hydrothermal alterations and mineral crystallizations they induced and data about the flow pathways in the exchanger.  相似文献   

16.
Reservoir quality is critical for sweet-spot evaluation in tight sandstone plays, but few studies have focused on the origin of authigenic minerals in tight sandstones and their impact on reservoir quality. This study integrates petrographic analysis, carbon and oxygen isotopic data and mercury injection capillary pressure data of the Upper Triassic Chang-7 tight sand reservoir samples in the Ordos Basin, China to understand the origin of authigenic minerals and the impact of authigenic minerals on reservoir quality. Carbonate minerals, including calcite, ferroan calcite and dolomite, and kaolinite, are the major authigenic minerals in the Chang-7 sandstone. They were derived from the chemical diagenetic alteration of detrital feldspar and biotite, with the involvement of ions that are believed to be primarily from the connate water in interstitial pore space of the interbedded mudstones. Meteoric water and organic fluids from hydrocarbon generation may also have been involved in the alteration processes of the minerals in the Chang-7 tight sandstone. The origin of kaolinite indicates that the porosity was increased by dissolution of detrital grains, offsetting the porosity loss from burial compaction. Authigenic minerals appear to have a weak correlation with pore structure, suggesting that the pore structure of the Chang-7 tight sandstone is not only controlled by major authigenic minerals but also affected by other geological factors.  相似文献   

17.
Marly rock is a sensitive rock group of landslides in the Three Gorges reservoir area, China. It is composed predominantly of carbonate and clay minerals, water–rock interaction (WRI) of which could activate landslides in the reservoir area. To study the mechanism by which WRI affects the mechanical properties of marly rock, samples were collected from two boreholes (depth 301.78 and 307.14 m) and slope surface. Then, laboratory tests were designed to study the quantitative relationship between mineral contents and mechanical properties of intact rock, to analyze both change process of mineral composition and microstructure under short-term and long-term WRI. Finally, the change in mechanical properties and its effect on slope stability are suggested. This study indicates that the uniaxial compressive strength and Poisson ratio can be estimated by linear regression equations: (1) σ c = 8.959 × (C/Q) ? 0.744 × CM + 58.516; (2) μ = 0.014 × (C/Q) ? 0.001 × CM + 0.234. The chemical reactions of WRI mainly included dissolution and ion exchange. On the slope surface, dissolution mainly acts on calcite, illite, dolomite, feldspar and other minerals dissolved in water. Underground, both chemical reactions of dissolution and ion exchange easily approach equilibrium with long-term seepage. Small-size minerals and micropores damage the stable microstructure of marly rock. These changes of minerals and microstructure can trigger shallow slope failure and develop deep creep deformation along some crash zones in the reservoir shoreline.  相似文献   

18.
Scanning Force Microscopy (SFM) was used to develop a method which can provide quantitative kinetic data of crystal growth and dissolution. Based on observations of single crystal faces in monolayer resolution, morphology and temperature dependent growth and dissolution rates can be obtained. From these kinetic data activation energies can be calculated and compared with existing theories. The experimental method works by extracting grown or dissolved terrace areas and step densities from image sequences taken at different temperatures. As an example, the method is applied for dissolution on the brucite (001) surface in acidic water (pH 2.7) within the temperature range of 21 to 35°C. At these conditions the dissolution rate depends nonlinearly on the step density and gives evidence for interstep interaction. The calculated activation energy for dissolution is 60 ± 12 kJ mol−1. With this high activation energy, dissolution cannot be regarded as a transport-controlled process, and is therefore surface controlled.  相似文献   

19.
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。  相似文献   

20.
The concentration of dissolved F did not change in long-term (four months) experiments on the interaction of crushed limestone and marl with water (at R/W = 1) at room temperature. The comparison of the activity products and equilibrium constants of the mineral dissolution reactions indicates that the experimental solutions were undersaturated with respect to fluorite and oversaturated with respect to F-apatite. The long-term existence of such unequilibrated solutions is explained by the steady state of the system at which the primary F-bearing mineral (fluorite, mica, or palygorskite) is transformed into a secondary one (F-apatite). The dissolved F concentration is controlled under these conditions by the ratios of the dissolution reaction rates for the primary mineral and the precipitation rate of the secondary one. In the experiments with the association fluorite + calcite + dolomite (duration up to seven months), the solution was saturated with respect to these minerals. Their dissolution constants were utilized to derive dependences of the activity of the dissolved F ion on the activities of the Ca, Mg, and carbonate ions in the solutions. The experimental data are consistent with these dependences. If the solution is saturated with respect to gypsum, the activity of the dissolved F ion should also depend on one more parameter: the activity of the sulfate ion.  相似文献   

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