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1.
A numerical model is presented to describe the evolution of fracture aperture (and related permeability) mediated by the competing chemical processes of pressure solution and free‐face dissolution/precipitation; pressure (dis)solution and precipitation effect net‐reduction in aperture and free‐face dissolution effects net‐increase. These processes are incorporated to examine coupled thermo‐hydro‐mechano‐chemo responses during a flow‐through experiment, and applied to reckon the effect of forced fluid injection within rock fractures at geothermal and petroleum sites. The model accommodates advection‐dominant transport systems by employing the Lagrangian–Eulerian method. This enables changes in aperture and solute concentration within a fracture to be followed with time for arbitrary driving effective stresses, fluid and rock temperatures, and fluid flow rates. This allows a systematic evaluation of evolving linked mechanical and chemical processes. Changes in fracture aperture and solute concentration tracked within a well‐constrained flow‐through test completed on a natural fracture in novaculite (Earth Planet. Sci. Lett. 2006, in press) are compared with the distributed parameter model. These results show relatively good agreement, excepting an enigmatic abrupt reduction in fracture aperture in the early experimental period, suggesting that other mechanisms such as mechanical creep and clogging induced by unanticipated local precipitation need to be quantified and incorporated. The model is applied to examine the evolution in fracture permeability for different inlet conditions, including localized (rather than distributed) injection. Predictions show the evolution of preferential flow paths driven by dissolution, and also define the sense of permeability evolution at field scale. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

2.
Examining the evolution of fracture permeability under stressed and temperature-elevated conditions, a series of flow-through experiments on a single rock fracture in granite has been conducted under confining pressures of 5 and 10 MPa, under differential water pressures ranging from 0.04 to 0.5 MPa, and at temperatures of 20–90 °C, for several hundred hours in each experiment. Measurements of fluid and dissolved mass fluxes, and post-experimental microscopy, were conducted to constrain the progress of mineral dissolution and/or precipitation and to examine its effect on transport properties. Generally, the fracture aperture monotonically decreased with time at room temperature, and reached a steady state in relatively short periods (i.e., <400 h). However, once the temperature was elevated to 90 °C, the aperture resumed decreasing and kept decreasing throughout the rest of the experimental periods. This reduction may result from the removal of the mineral mass from the bridging asperities within the fracture. Post-experimental observations by scanning electron microscopy, coupled with energy dispersive X-ray spectroscopy (SEM-EDX), revealed the formation of several kinds of secondary minerals such as silica and calcite. However, the precipitated minerals seemed to have had little influence on the flow characteristics within the fracture, because the precipitation was limited to quite local and small areas. The evolving rates and ultimate magnitudes of the fracture aperture are likely to be controlled by the stress exerted over the contacting asperities and temperatures, and by the prescribed flow conditions. Thus, this complex behavior should be attributed to the coupled chemically- and mechanically-induced effect. A coupled chemo–mechano conceptual model, accounting for pressure and free-face dissolutions, is presented in this paper to follow the evolution of the fracture permeability observed in the flow-through experiments. This model addresses the two dissolution processes at the contacting asperities and the free walls within the fractures, and is also capable of describing multi-mineral dissolution behavior. The model shows that the evolution of a fracture aperture (or related permeability) and of element concentrations may be followed with time under arbitrary temperature and pressure conditions. The model predictions for the evolving fracture aperture and elements concentrations show a relatively good agreement with the experimental measurements, although it is not possible to replicate the abrupt reduction observed in the early periods of the experiments, which is likely to be due to an unaccounted mechanism of more stress-mediated fracture compaction driven by the fracturing of the propping asperities.  相似文献   

3.
A numerical model is developed for investigating the evolution of fracture permeability in a coupled fracture-matrix system in the presence of fracture-skin with simultaneous colloidal and bacterial tr...  相似文献   

4.
Structural investigations, integrated with X‐ray diffraction, fluid inclusion microthermometry and oxygen‐stable isotope analyses are used to reconstruct the deformation history and the palaeo‐fluid circulation during formation of the low‐grade, turbidite‐dominated Early Palaeozoic Robertson Bay accretionary complex of north Victoria Land (Antarctica). Evidence for progressive deformation is elucidated by analysing the textural fabric of chronologically distinct, thrust‐related quartz vein generations, incrementally developed during progressive shortening and thickening of the Robertson Bay accretionary complex. Our data attest that orogenic deformation was mainly controlled by dissolution–precipitation creep, modulated by stress‐ and strain‐rate‐dependent fluid pressure cycling, associated with local and regional permeability variations induced by the distribution and evolution of the fracture network during regional thrusting. Fracture‐related fluid pathways constituted efficient conduits for episodic fluid flow. The dominant migrating fluid was pre‐to‐syn‐folding and associated with the migration of warm (160–200 °C) nitrogen‐ and carbonic (CO2 and CH4)‐bearing fluids. Both fluid advection and diffusive mass transfer are recognized as operative mechanisms for fluid–rock interaction and vein formation during continuous shortening. In particular, fluid–rock interaction was the consequence of dissolution–precipitation creep assisted by tectonically driven cooling fluids moving through the rock section as a result of seismic pumping. The most likely source of the migrating fluids would be the frontal part of the growing accretionary complex, where fluids from the deep levels in the hinterland are driven trough channelization operated by the thrust‐related fracture (fault) systems.  相似文献   

5.
This paper mainly deals with the theoretical aspects of chemical dissolution‐front instability problems in two‐dimensional fluid‐saturated porous media under non‐isothermal conditions. In the case of the mineral dissolution ratio (that is defined as the ratio of the dissolved‐mineral equilibrium concentration in the pore fluid to the molar concentration of the dissolvable mineral in the solid matrix of the fluid‐saturated porous medium) approaching zero, the corresponding critical condition has been mathematically derived when temperature variation effects are considered. As a complementary tool, the computational simulation method is used to simulate the morphological evolution of chemical dissolution fronts in two‐dimensional fluid‐saturated porous media under non‐isothermal conditions. The related theoretical and numerical results have demonstrated that: (i) a temperature increase in a non‐isothermal chemical dissolution system can have some influence on the propagation speed of the planar chemical dissolution front in the system. Generally, the chemical dissolution front in the non‐isothermal chemical dissolution system propagates slower than that in the counterpart isothermal chemical dissolution system when the temperature of the non‐isothermal chemical dissolution system is higher than that of the counterpart isothermal chemical dissolution system; (ii) a temperature increase in the non‐isothermal chemical dissolution system can stabilize the chemical dissolution front propagating in the system, because it can cause a decrease in the Zhao number of the system but does not affect the critical Zhao number of the system; and (iii) the temperature gradient in the upstream direction of a chemical dissolution front is smaller than that in the downstream direction of the chemical dissolution front when the non‐isothermal chemical dissolution system is supercritical. Copyright © 2014 John Wiley & Sons, Ltd.  相似文献   

6.
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.  相似文献   

7.
In the Earth's upper crust, where aqueous fluids can circulate freely, most mineral transformations are controlled by the coupling between the dissolution of a mineral that releases chemical species into the fluid and precipitation of new minerals that contain some of the released species in their crystal structure, the coupled process being driven by a reduction of the total free-energy of the system. Such coupled dissolution-precipitation processes occur at the fluid-mineral interface where the chemical gradients are highest and heterogeneous nucleation can be promoted, therefore controlling the growth kinetics of the new minerals. Time-lapse nanoscale imaging using Atomic Force Microscopy (AFM) can monitor the whole coupled process under in situ conditions and allow identifying the time scales involved and the controlling parameters. We have performed a series of experiments on carbonate minerals (calcite, siderite, dolomite and magnesite) where dissolution of the carbonate and precipitation of a new mineral was imaged and followed through time. In the presence of various species in the reacting fluid (e. g. antimony, selenium, arsenic, phosphate), the calcium released during calcite dissolution binds with these species to form new minerals that sequester these hazardous species in the form of a stable solid phase. For siderite, the coupling involves the release of Fe2+ ions that subsequently become oxidized and then precipitate in the form of FeIII oxyhydroxides. For dolomite and magnesite, dissolution in the presence of pure water (undersaturated with any possible phase) results in the immediate precipitation of hydrated Mg-carbonate phases. In all these systems, dissolution and precipitation are coupled and occur directly in a boundary layer at the carbonate surface. Scaling arguments demonstrate that the thickness of this boundary layer is controlled by the rate of carbonate dissolution, the equilibrium concentration of the precipitates and the kinetics of diffusion of species in a boundary layer. From these parameters a characteristic time scale and a characteristic length scale of the boundary layer can be derived. This boundary layer grows with time and never reaches a steady state thickness as long as dissolution of the carbonate is faster than precipitation of the new mineral. At ambient temperature, the surface reactions of these dissolving carbonates occur on time-scales of the order of seconds to minutes, indicating the rapid surface rearrangement of carbonates in the presence of aqueous fluids. As a consequence, many carbonate-fluid reactions in low temperature environments are controlled by local thermodynamic equilibria rather than by the global equilibrium in the whole system.  相似文献   

8.
碳酸盐岩单裂隙渗流-溶蚀耦合模型及其参数敏感性分析   总被引：1，自引：1，他引：0  
岩溶地下水系统是由碳酸盐岩裂隙含水介质演化形成的,系统初始的裂隙网络介质特征及边界条件决定了其演化过程。为揭示岩溶系统演化过程中裂隙介质特征和边界条件的影响程度,建立了裂隙溶蚀扩展的渗流-溶蚀耦合模型,并对不同边界条件下不同隙宽的单裂隙溶蚀扩展特征进行了模拟分析。结果表明:裂隙溶蚀扩展受水的侵蚀性(CO2分压)、水动力条件(水力梯度)、裂隙介质特征(裂隙初始隙宽)等综合作用影响,Ca2+的平衡浓度、水力梯度以及裂隙初始隙宽等参数的增加均能促进裂隙的快速扩展。在这些参数中,初始隙宽B0对岩溶发育的影响最为敏感,水力梯度J和Ca2+平衡浓度Ceq对岩溶发育具有相同的敏感性;此外,随着各参数值的不断增大,参数变化对岩溶发育的敏感程度越来越低。  相似文献   

9.
An established engineering model is used to identify conditions where diffusion controls the dissolution of quartz and forsterite in packed beds. The model shows that diffusion control is favored at low advection flux, large grain size, high temperature, and high pH (if the reaction consumes H+). Quartz dissolution is chemical reaction controlled for most geochemically reasonable combinations of temperature, grain size, and flow rate. On the other hand, forsterite dissolution rates can be diffusion controlled for typical advection fluxes, grain sizes, temperatures, and pH’s. The apparent activation energy for diffusion-controlled reactions in a packed bed is much higher than the <∼20 kJ/mol value that is often used to identify diffusion controlled reactions. The models are quite general and can be adapted to deal with other mineral dissolution and precipitation reactions.  相似文献   

10.
This paper analyses the problem of a fluid‐driven fracture propagating in an impermeable, linear elastic rock with finite toughness. The fracture is driven by injection of an incompressible viscous fluid with power‐law rheology. The relation between the fracture opening and the internal fluid pressure and the fracture propagation in mobile equilibrium are described by equations of linear elastic fracture mechanics (LEFM), and the flow of fluid inside the fracture is governed by the lubrication theory. It is shown that for shear‐thinning fracturing fluids, the fracture propagation regime evolves in time from the toughness‐ to the viscosity‐dominated regime. In the former, dissipation in the viscous fluid flow is negligible compared to the dissipation in extending the fracture in the rock, and in the later, the opposite holds. Corresponding self‐similar asymptotic solutions are given by the zero‐viscosity and zero‐toughness (J. Numer. Anal. Meth. Geomech. 2002; 26 :579–604) solutions, respectively. A transient solution in terms of the crack length, the fracture opening, and the net fluid pressure, which describes the fracture evolution from the early‐time (toughness‐dominated) to the large‐time (viscosity‐dominated) asymptote is presented and some of the implications for the practical range of parameters are discussed. Copyright © 2006 John Wiley & Sons, Ltd.  相似文献   

11.
Detailed electron microprobe analyses of phyllosilicates in crenulated phyllites from south‐eastern Vermont show that grain‐scale zoning is common, and sympathetic zoning in adjacent minerals is nearly universal. We interpret this to reflect a pressure‐solution mechanism for cleavage development, where precipitation from a very small fluid reservoir fractionated that fluid. Multiple analyses along single muscovite, biotite and chlorite grains (30–200 μm in length) show zoning patterns indicating Tschermakitic substitutions in muscovite and both Tschermakitic and di/trioctahedral substitutions in biotite and chlorite. Using cross‐cutting relationships and mineral chemistry it is shown that these patterns persist in cleavages produced at metamorphic conditions of chlorite‐grade, chlorite‐grade overprinted by biotite‐grade and biotite‐grade. Zoning patterns are comparable in all three settings, requiring a similar cleavage‐forming mechanism independent of metamorphic grade. Moreover, the use of 40Ar/39Ar geochronology demonstrates this is true regardless of age. Furthermore, samples with chlorite‐grade cleavages overprinted by biotite porphyroblasts suggest the closure temperatures for the diffusion of Al, Si, Mg and Fe ions are greater than the temperature of the biotite isograd (>～400 °C). Parallel and smoothly fanning tie lines produced by coexisting muscovite–chlorite, and muscovite–biotite pairs on compositional diagrams demonstrate effectively instantaneous chemical equilibrium and probably indicate simultaneous crystallization. These results do not support theories suggesting cleavages form in fluid‐dominated systems. If crenulation cleavages formed in systems in which the chemical potentials of all major components are fixed by an external reservoir, then the compositions of individual grains defining these cleavages would be uniform. On the contrary, the fine‐scale chemical zoning observed probably reflects a grain‐scale process consistent with a pressure‐solution mechanism in which the aqueous activities of major components are defined by local dissolution and precipitation. Thus the role of fluids was probably limited to one of catalysing pressure‐solution and fluids apparently did not drive cleavage development.  相似文献   

12.
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   

13.
Geochemistry of soil, soil water, and soil gas was characterized in representative soil profiles of three Michigan watersheds. Because of differences in source regions, parent materials in the Upper Peninsula of Michigan (the Tahquamenon watershed) contain only silicates, while those in the Lower Peninsula (the Cheboygan and the Huron watersheds) have significant mixtures of silicate and carbonate minerals. These differences in soil mineralogy and climate conditions permit us to examine controls on carbonate and silicate mineral weathering rates and to better define the importance of silicate versus carbonate dissolution in the early stage of soil-water cation acquisition.Soil waters of the Tahquamenon watershed are the most dilute; solutes reflect amphibole and plagioclase dissolution along with significant contributions from atmospheric precipitation sources. Soil waters in the Cheboygan and the Huron watersheds begin their evolution as relatively dilute solutions dominated by silicate weathering in shallow carbonate-free soil horizons. Here, silicate dissolution is rapid and reaction rates dominantly are controlled by mineral abundances. In the deeper soil horizons, silicate dissolution slows down and soil-water chemistry is dominated by calcite and dolomite weathering, where solutions reach equilibrium with carbonate minerals within the soil profile. Thus, carbonate weathering intensities are dominantly controlled by annual precipitation, temperature and soil pCO2. Results of a conceptual model support these field observations, implying that dolomite and calcite are dissolving at a similar rate, and further dissolution of more soluble dolomite after calcite equilibrium produces higher dissolved inorganic carbon concentrations and a Mg2+/Ca2+ ratio of 0.4.Mass balance calculations show that overall, silicate minerals and atmospheric inputs generally contribute <10% of Ca2+ and Mg2+ in natural waters. Dolomite dissolution appears to be a major process, rivaling calcite dissolution as a control on divalent cation and inorganic carbon contents of soil waters. Furthermore, the fraction of Mg2+ derived from silicate mineral weathering is much smaller than most of the values previously estimated from riverine chemistry.  相似文献   

14.
渗流-化学溶解耦合作用下岩石单裂隙渗透特性研究   总被引：3，自引：0，他引：3  
为揭示在渗流-化学溶解耦合作用下单裂隙渗透特性的变化规律,建立了描述二维渗流-化学溶解耦合作用的偏微分方程组,并利用COMSOL Multiphysics软件成功地求解该方程组。首先,模拟了文献[1]中的盐岩渗流-溶解耦合渗流试验结果,数值模拟结果与试验结果较为吻合,验证了数学模型的正确性和有效性。然后,利用分形理论生成了一个粗糙的裂隙面数字模型,着重分析了二维石灰岩粗糙裂隙面在水流、矿物溶解和输运过程中其渗透特性的变化规律。数值分析显示,（1）溶质浓度对裂隙面的溶解具有非常重要的作用,从而水流进口端的溶解厚度比出口端大得多。（2）裂隙的整体渗透性在初始时刻增加较慢,随着裂隙开度的增大和贯通,溶解速度会逐渐增大,是一个加速的过程。  相似文献   

15.
《Applied Geochemistry》2003,18(10):1555-1571
In the context of the proposed low- and intermediate-level radioactive waste repository at Wellenberg (Switzerland), calculations simulating the interaction between hyperalkaline solutions and a fractured marl, at 25 °C, have been performed. The aim of these calculations is to evaluate the possible effects of mineral dissolution and precipitation on porosity and permeability changes in such a fractured marl, and their impact on repository performance. Solute transport and chemical reaction are considered in both a high-permeability zone (fracture), where advection is important, and the wall rock, where diffusion is the dominant transport mechanism. The mineral reactions are promoted by the interaction between hyperalkaline solutions derived from the degradation of cement (a major component of the engineered barrier system in the repository) and the host rock. Both diffusive/dispersive and advective solute transport are taken into account in the calculations. Mineral reactions are described by kinetic rate laws. The fluid flow system under consideration is a two-dimensional porous medium (marl, 1% porosity), with a high-permeability zone simulating a fracture (10% porosity) crossing the domain. The dimensions of the domain are 6 m per 1 m, and the fracture width is 10 cm. The fluid flow field is updated during the course of the simulations. Permeabilities are updated according to Kozeny's equation. The composition of the solutions entering the domain is derived from modeling studies of the degradation of cement under the conditions at the proposed underground repository at Wellenberg. Two different cases have been considered in the calculations. These 2 cases are representative of 2 different stages in the process of degradation of cement (pH 13.5 and pH 12.5). In both cases, the flow velocity in the fracture diminishes with time, due to a decrease in porosity. This decrease in porosity is caused by the precipitation of calcite (replacement of dolomite by calcite) and other secondary minerals (brucite, sepiolite, analcime, natrolite, tobermorite). However, the decrease in porosity and flow velocity is much more pronounced in the lower pH case. The extent of the zone of mineral alteration along the fracture is also much more limited in the lower pH case. The reduction of porosity in the fractures would be highly beneficial for repository performance, since it would mean that the solutions coming from the repository and potentially carrying radionuclides in solution would have to flow through low-conductive rock before they would be able to get to higher-conductive features. The biggest uncertainty in the reaction rates used in the calculations arises from the surface areas of the primary minerals. Additional calculations making use of smaller surface areas have also been performed. The results show that the smaller surface areas (and therefore smaller reaction rates) result in a smaller reactivity of the system and smaller porosity changes.  相似文献   

16.
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   

17.
Pore water chemistry and 234U/238U activity ratios from fine-grained sediment cored by the Ocean Drilling Project at Site 984 in the North Atlantic were used as constraints in modeling in situ rates of plagioclase dissolution with the multicomponent reactive transport code Crunch. The reactive transport model includes a solid-solution formulation to enable the use of the 234U/238U activity ratios in the solid and fluid as a tracer of mineral dissolution. The isotopic profiles are combined with profiles of the major element chemistry (especially alkalinity and calcium) to determine whether the apparent discrepancy between laboratory and field dissolution rates still exists when a mechanistic reactive transport model is used to interpret rates in a natural system. A suite of reactions, including sulfate reduction and methane production, anaerobic methane oxidation, CaCO3 precipitation, dissolution of plagioclase, and precipitation of secondary clay minerals, along with diffusive transport and fluid and solid burial, control the pore fluid chemistry in Site 984 sediments. The surface area of plagioclase in intimate contact with the pore fluid is estimated to be 6.9 m2/g based on both grain geometry and on the depletion of 234U/238U in the sediment via α-recoil loss. Various rate laws for plagioclase dissolution are considered in the modeling, including those based on (1) a linear transition state theory (TST) model, (2) a nonlinear dependence on the undersaturation of the pore water with respect to plagioclase, and (3) the effect of inhibition by dissolved aluminum. The major element and isotopic methods predict similar dissolution rate constants if additional lowering of the pore water 234U/238U activity ratio is attributed to isotopic exchange via recrystallization of marine calcite, which makes up about 10-20% of the Site 984 sediment. The calculated dissolution rate for plagioclase corresponds to a rate constant that is about 102 to 105 times smaller than the laboratory-measured value, with the value depending primarily on the deviation from equilibrium. The reactive transport simulations demonstrate that the degree of undersaturation of the pore fluid with respect to plagioclase depends strongly on the rate of authigenic clay precipitation and the solubility of the clay minerals. The observed discrepancy is greatest for the linear TST model (105), less substantial with the Al-inhibition formulation (103), and decreases further if the clay minerals precipitate more slowly or as highly soluble precursor minerals (102). However, even several orders of magnitude variation in either the clay solubility or clay precipitation rates cannot completely account for the entire discrepancy while still matching pore water aluminum and silica data, indicating that the mineral dissolution rate conundrum must be attributed in large part to the gradual loss of reactive sites on silicate surfaces with time. The results imply that methods of mineral surface characterization that provide direct measurements of the bulk surface reactivity are necessary to accurately predict natural dissolution rates.  相似文献   

18.
It is widely proposed that tectonic pressure (the difference between the mean stress and the pressure arising from a lithostatic load) is large, and has a significant influence on mineral phase equilibria in deforming metamorphic rocks. The implication/assertion is that the mean stress is equivalent to the thermodynamic pressure which characterizes mineral phase equilibria and is a measure of how the energy changes as the volume changes. We distinguish two useful thermodynamic pressures. The first is an equilibrium thermodynamic pressure, characteristic of non‐dissipative systems and related directly to equilibrium values of the chemical potentials that define stable, equilibrium phase assemblages. The second is a non‐equilibrium thermodynamic pressure characteristic of dissipative systems with zero net entropy production and related to non‐equilibrium chemical potentials that define stable non‐equilibrium phase assemblages. In many dissipative metamorphic systems discussed in the literature, the concepts of thermodynamic pressure and chemical potential are not usefully defined because the system is not at equilibrium and/or no volume change is involved in the deformation. The conclusion of this note is that the influence of tectonic pressure on phase equilibria is minor. The role of tectonic pressure is an important issue but is only relevant to phase equilibrium when an equilibrium thermodynamic pressure can be defined; in such cases, the influence of tectonic pressure is small compared to many proposals in the literature. Except for elastic deformations, the mean stress is not useful in discussing mineral phase equilibrium.  相似文献   

19.
We use numerical modelling codes to simulate aspects of some current hypotheses for the origin of gold deposits and hydrothermal systems in the Yilgarn Craton of Western Australia. In particular, we investigate conceptual models advocating vertically continuous hydrothermal systems as well as those invoking extensive lateral flow and possible links with advection of heat by late orogenic granitic magmatism. Numerical models of part of the Eastern Goldfields Province and Southern Cross Province have been built with FLAC3D, to simulate crustal‐scale coupled interaction between deformation and fluid flow. These illustrate the potential for fluid focusing and mixing in shear zones, including downflow of meteoric water, lateral fluid flow driven by topographic elevation and upwards flow of fluids derived from melting and metamorphism in the deep crust. In some cases, downflow also occurs within the middle crust, at depths where fluid influx might trigger melting if the geothermal gradient were appropriate. The models indicate that tectonic wedging within a layered crust and diverging thrust systems that generate ‘pop‐up’ wedges may be important in facilitating efficient fluid upflow and downflow during uplift, while topographic elevation related to asymmetric thrust migration and loading tends to promote lateral fluid flow. However, the effect of topography appears more important than the precise depth or location of the site of fluid production in the deep crust. The effects of thermal convection and fluid‐fluid interaction have also been numerically modelled for a simplified section across the Kalgoorlie Terrane. Modelling under both hydrostatic and lithostatically overpressured pore‐pressure gradients has effectively delineated domains of convective fluid flow within the middle and upper crust, and has identified two generic sites that are favourable for fluid mixing, notably hangingwall and footwall environments in major shear zones, such as the Bardoc Shear, and in broad antiforms, such as the Goongarrie ‐ Mt Pleasant Antiform. The thermal effect of small plutons embedded in a regional metamorphic regime can cause significant lateral displacement of fluid convection patterns, over distances greater than pluton diameter, as well as more proximal effects on precipitation and dissolution of mineral species. However, these results are highly dependent on the pore‐pressure gradient and the permeability structure of the crust, and require magmatic and metamorphic fluid generation to be precisely timed with respect to deformation, thus reinforcing the dynamic feedback between deformation, magmatism and fluid production and migration.  相似文献   

20.
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   

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