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1.
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2.
A mathematical model is presented that describes the effects of pore fluid aqueous diffusion and reaction rate on the isotopic exchange between fluids and rocks in reactive geo-hydrological systems where flow is primarily through fractures. The model describes a simple system with parallel equidistant fractures, and chemical transport in the matrix slabs between fractures by aqueous diffusion through a stagnant pore fluid. The solid matrix exchanges isotopes with pore fluid by solution-precipitation at a rate characterized by a time constant, R (yr−1), which is an adjustable parameter. The effects of reaction on the isotopes of a particular element in the fracture fluid are shown to depend on the ratio of the diffusive reaction length for that element (L) to the fracture spacing (b). The reaction length depends on the solid-fluid exchange rate within the matrix, the partitioning of the element between the matrix pore fluid and the matrix solid phase, the porosity and density of the matrix, and the aqueous diffusivity. For L/b < 0.3, fluid-rock isotopic exchange is effectively reduced by a factor of 2L/b relative to a standard porous flow (single porosity) model. For L/b > 1, the parallel fracture model is no different from a porous flow model. If isotopic data are available for two or more elements with different L values, it may be possible to use the model with appropriate isotopic measurements to estimate the spacing of the primary fluid-carrying fractures in natural fluid-rock systems. Examples are given using Sr and O isotopic data from mid-ocean ridge (MOR) hydrothermal vent fluids and Sr isotopes in groundwater aquifers hosted by fractured basalt. The available data for MOR systems are consistent with average fracture spacing of 1-4 m. The groundwater data suggest larger effective fracture spacing, in the range 50-500 m. In general, for fractured rock systems, the effects of fracture-matrix diffusive exchange must be considered when comparing isotopic exchange effects for different elements, as well as for estimating water age using radioactive and cosmogenic isotopes.  相似文献   

3.
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4.
Based on the fluid phase equilibrium of the C-O-H system, the compositions of various fluid phases under high temperatures and pressures have been calculated in terms of the available thermodynamic data and newP-V-T data and on the assumption ofP T= ΣPi in this paper. The results indicate that in this system there are 5 major fluid phases in different proportions at variousT andP. CH4 is the dominant phase (about 70%) under relatively lowerT andP. Its proportion obviously decreases with increasingT, P andfo2. The results provide sufficient theoretical grounds for discussing the possibility of CH4 formation and the physical-chemical conditions of its stable occurrence and proportion in the geological environment.  相似文献   

5.
The problem of finite element simulation of incompressible fluid flow in porous medium is considered. The porous medium is characterized by the X‐ray microtomography technique in three dimensions. The finite calculus‐based stabilization technique is reviewed to implement the equal order finite element interpolation functions for both velocity and pressure. A noble preconditioner, the nodal block diagonal preconditioner, is considered whose performance is thoroughly investigated. Combining this preconditioner with a standard iterative solver during the computational homogenization procedure, it is possible to carry out the large‐scale fluid flow simulation for estimating permeability of the porous medium with reasonable accuracy and reliability. Copyright © 2013 John Wiley & Sons, Ltd.  相似文献   

6.
The 87Sr/86Sr ratios and Sr concentrations in sediment and pore fluids are used to evaluate the rates of calcite recrystallization at ODP Site 807A on the Ontong Java Plateau, an 800-meter thick section of carbonate ooze and chalk. A numerical model is used to evaluate the pore fluid chemistry and Sr isotopes in an accumulating section. The deduced calcite recrystallization rate is 2% per million years (%/Myr) near the top of the section and decreases systematically in older parts of the section such that the rate is close to 0.1/age (in years). The deduced recrystallization rates have important implications for the interpretation of Ca and Mg concentration profiles in the pore fluids. The effect of calcite recrystallization on pore fluid chemistry is described by the reaction length, L, which varies by element, and depends on the concentration in pore fluid and solid. When L is small compared to the thickness of the sedimentary section, the pore fluid concentration is controlled by equilibrium or steady-state exchange with the solid phase, except within a distance L of the sediment-water interface. When L is large relative to the thickness of sediment, the pore fluid concentration is mostly controlled by the boundary conditions and diffusion. The values of L for Ca, Sr, and Mg are of order 15, 150, and 1500 meters, respectively. LSr is derived from isotopic data and modeling, and allows us to infer the values of LCa and LMg. The small value for LCa indicates that pore fluid Ca concentrations, which gradually increase down section, must be equilibrium values that are maintained by solution-precipitation exchange with calcite and do not reflect Ca sources within or below the sediment column. The pore fluid Ca measurements and measured alkalinity allow us to calculate the in situ pH in the pore fluids, which decreases from 7.6 near the sediment-water interface to 7.1 ± 0.1 at 400-800 mbsf. While the calculated pH values are in agreement with some of the values measured during ODP Leg 130, most of the measurements are artifacts. The large value for LMg indicates that the pore fluid Mg concentrations at 807A are not controlled by calcite-fluid equilibrium but instead are determined by the changing Mg concentration of seawater during deposition, modified by aqueous diffusion in the pore fluids. We use the pore fluid Mg concentration profile at Site 807A to retrieve a global record for seawater Mg over the past 35 Myr, which shows that seawater Mg has increased rapidly over the past 10 Myr, rather than gradually over the past 60 Myr. This observation suggests that the Cenozoic rise in seawater Mg is controlled by continental weathering inputs rather than by exchange with oceanic crust. The relationship determined between reaction rate and age in silicates and carbonates is strikingly similar, which suggests that reaction affinity is not the primary determinant of silicate dissolution rates in nature.  相似文献   

7.
The bulk salinity cannot be directly obtained from the dissolution temperatures of halite in highly saline fluid inclusions that contain solid, liquid, and vapour at room temperature. At least two of the following independent parameters must be determined to estimate the bulk composition and density of these inclusions: 1. dissolution temperature of halite in the presence of vapour; 2. total homogenization temperature of liquid and vapour; and 3. volume fraction of the vapour phase. A new V m -x diagram for phase stabilities in the H2O-NaCl system has been constructed to obtain these bulk fluid properties from inclusions that homogenize liquid and vapour phase at higher temperatures than dissolution of halite.  相似文献   

8.
The Xitieshan terrane, located in the central part of the North Qaidam ultrahigh pressure (UHP) metamorphic belt, China, is mainly composed of orthogneiss and paragneiss and a few intercalated eclogite layers and boudins. Based on their bulk-rock TiO2-contents, the eclogites can be subdivided into a high-Ti group (TiO2 > 2%) and a low-Ti group (TiO2 < 2%). Whole-rock major and trace element analyses revealed that the protoliths of the low-Ti eclogites are normal-type mid-ocean ridge basalts (N-MORB), whereas those of the high-Ti eclogites are either enriched-type mid-ocean ridge basalts (E-MORB) or near ridge seamount basalts, respectively. The Sr–Nd isotopes of eclogites of both groups are similar to those of MORB. Those of the low-Ti eclogites are characterized by positive εNd(T) and restricted ISr values and therefore provide further evidence for the formation of the protoliths of the eclogites in an oceanic environment. On the other hand, the Sr–Nd isotopes of high-Ti eclogites show mainly positive but also some negative εNd(T) values and relatively broadly distributed ISr values, indicating minor crustal contamination of the ocean floor basalts. Considering available 750–877 Ma protolith ages preserved in zircon cores, it is inferred that some of the eclogites derived from Neoproterozoic protoliths were emplaced onto the crust far ahead of the Paleozoic deep subduction, while the other eclogites originate from a different oceanic crust, e.g., the Paleo-Qilian ocean, indicating multiple orogenies in the geological history of the Xitieshan terrane, China.Whole-rock and in-situ LA-ICP-MS mineral trace element analyses of eclogites revealed two stages of fluid behavior during retrogression that correspond to the two exhumation stages uncovered by phase equilibrium calculations. The mineral scale trace element distributions and trace element inheritance of newly formed amphibole from its precursors indicate that, at the peak metamorphic stage (M1) and at the earlier (eclogite facies) overprint (M2), the fluid was internally controlled by the rock itself. Within a mafic lens, the amount of water-soluble elements (e.g., Rb, Sr, Ba, U, Pb and LREE), observed in the whole-rock compositions as well as in amphiboles, increases from the core (phengite-bearing eclogite) to the rim (amphibolite) and implies an external fluid source for the amphibolite facies retrogression (M3) which should be helpful for the final exhumation of UHP eclogite.  相似文献   

9.
Measurements of the final dissociation temperature of gas-clathrate hydrates (TmCLA) are routinely used to determine the salinity of fluid inclusions which contain a volatile component in addition to water. Traditionally, experimental data are used to quantitatively relate TmCLA to the inclusion electrolyte concentration. Because of limitations in the experimental database, however, this method has hitherto not been applicable to the multivolatile fluid inclusions that are common in crustal rocks.A general solution to this problem is provided by statistical thermodynamics predictions of multivolatile clathrate stability. Published theoretical models explicitly account for the effect of aqueous NaCl in depressing the stability of clathrates composed of any mixture of CO2, N2, H2S, CH4 and higher-order hydrocarbons. Analysis of phase relations in complex clathrate systems shows that such theoretical predictions yield model salinities if the following fluid inclusion data are available: (1) the identity of the phase assemblage at TmCLA, (2) the relative concentrations of the volatile species, and (3) either the homogenization temperature of the volatile fluid fraction (bubble point or dew point, either stable or metastable), or an independent estimate of internal pressure at TmCLA. Additional data on fluid inclusion cation ratios can be incorporated in the calculations to recast equivalent weight percent aqueous NaCl in terms of effective electrolyte concentrations.New experimental data on mixed N2-CO2 clathrates, obtained from synthetic fluid inclusions, provide a test of both the model predictions and of the analytical procedure proposed for natural fluid inclusions. While the accuracy of the predictions varies between volatile compositions, the uncertainties in the salinities derived from the statistical thermodynamics method are generally of the order acceptable for geochemical applications. Applications to multivolatile, multi-electrolyte fluid inclusions from gold-quartz deposits illustrate the practical operations involved in determining salinity.  相似文献   

10.
Aquifer contamination by organic chemicals in subsurface flow through soils due to leaking underground storage tanks filled with organic fluids is an important groundwater pollution problem. The problem involves transport of a chemical pollutant through soils via flow of three immiscible fluid phases: namely air, water and an organic fluid. In this paper, assuming the air phase is under constant atmospheric pressure, the flow field is described by two coupled equations for the water and the organic fluid flow taking interphase mass transfer into account. The transport equations for the contaminant in all the three phases are derived and assuming partition equilibrium coefficients, a single convective – dispersive mass transport equation is obtained. A finite element formulation corresponding to the coupled differential equations governing flow and mass transport in the three fluid phase porous medium system with constant air phase pressure is presented. Relevant constitutive relationships for fluid conductivities and saturations as function of fluid pressures lead to non-linear material coefficients in the formulation. A general time-integration scheme and iteration by a modified Picard method to handle the non-linear properties are used to solve the resulting finite element equations. Laboratory tests were conducted on a soil column initially saturated with water and displaced by p-cymene (a benzene-derivative hydrocarbon) under constant pressure. The same experimental procedure is simulated by the finite element programme to observe the numerical model behaviour and compare the results with those obtained in the tests. The numerical data agreed well with the observed outflow data, and thus validating the formulation. A hypothetical field case involving leakage of organic fluid in a buried underground storage tank and the subsequent transport of an organic compound (benzene) is analysed and the nature of the plume spread is discussed.  相似文献   

11.
One dimensional solutions for the classic critical upward seepage gradient/quick condition and the time rate of consolidation problems are obtained using coupled routines for the finite volume method (FVM) and discrete element method (DEM), and the results compared with the analytical solutions. The two phase flow in a system composed of fluid and solid is simulated with the fluid phase modeled by solving the averaged Navier–Stokes equation using the FVM and the solid phase is modeled using the DEM. A framework is described for the coupling of two open source computer codes: YADE-OpenDEM for the discrete element method and OpenFOAM for the computational fluid dynamics. The particle–fluid interaction is quantified using a semi-empirical relationship proposed by Ergun [12]. The two classical verification problems are used to explore issues encountered when using coupled flow DEM codes, namely, the appropriate time step size for both the fluid and mechanical solution processes, the choice of the viscous damping coefficient, and the number of solid particles per finite fluid volume.  相似文献   

12.
Sulphate concentrations have been determined in fluid inclusions by Raman spectroscopy using the M.O.L.E. microprobe after verifying that the sulphate determination is proportional to the total sulphate in the aqueous phase. Comparison of miSO4. values in primary fluid inclusions with associated mother brine from actual solar salt works demonstrates their chemical equivalence.Keuper halite of marine origin has also been studied. The inclusions contain solid phases: anhydrite and possibly gypsum and glauberite as well. The moiality of the total dissolved sulphate in the aqueous phase is lower than that obtained during present sea-water evaporation at the halite stage of precipitation. Some geochemical hypotheses are proposed to account for this anomaly.  相似文献   

13.
If anatexis takes place in the presence of an immiscible volatile-rich fluid phase, the behaviour of a trace element depends not only on partition coefficients Di ? between mineral i and silicate liquid, but also on coefficients Di f between mineral i and fluid. The limited experimental data available, as well as theoretical arguments, suggest that for common minerals these coefficients differ, in some cases (REE) notably.Theory has been developed to permit calculation of concentration variations with the fraction F of rock melted, if D-values are known. In its present state this theory neglects the influence of T, P and composition variations in liquid and fluid on the D-values: if such variations can be expressed as functions of F, appropriate modifications can be made. The theory also neglects the effects of T and P on the solubility of fluid in liquid and the resulting modifications to phase petrology, by assuming simply that a given mass of rock melts in the presence of a mass proportion v of fluid. By choosing different values of v, from 0 (dry melting) to 100 (large fluid excess), the response of the trace element concentrations can be followed, beginning with concentration co in the unmelted rock. Such treatment is highly idealised, but serves to indicate some limits on what can occur.  相似文献   

14.
The equations relating element distribution and pH are derived for systems containing an ideal solid solution in equilibrium with an ideal aqueous solution, assuming no polymeric complexes form in the aqueous solution and the solid solution does not contain molecular units with multiple atoms of the substituting elements. These expressions demonstrate that the ratio of the partition coefficients describing element distribution for a system containing a multi-component solid solution is inversely proportional to the solubilities of the end member components at any given pH raised to the power equal to the ratio of the sum of the stoichiometric coefficients of the end-member salt to the stoichiometric coefficient of the substituting radical. The coefficient describing distribution between the aqueous phase and a two-component solid solution is equal to the inverse of the ratio of the end member solubilities raised to the above power. Element distribution between the two phases will be homogenous at any pH resulting in identical solubilities for the two end-member components, and a reversal in relative solubilities will result in a corresponding reversal in the element preferentially incorporated into the solid solution. Because of the dependence of element distribution on pH, a crystal could develop both zoning and reverse zoning as a result of changes in pH. The distribution coefficient could provide information regarding the pH of the aqueous solution at the time of mineral formation if independent evidence establishes the ratio of end-member components in the aqueous phase. The equations describing element distribution may be expressed in terms of the solubility products of the end-member components and the ionization constants of the substituting radicals. Based on the relative values of the ionization constants, pH intervals can be established in which only the concentration of a single complex for each substituting radical need be considered. Within such an interval, the curve of the log of the distribution coefficient vs. pH is linear with a slope equal to the difference in the charges of the two complexes. This approach to the examination of element distribution is developed in some detail for the geologically important case of a two component solid solution having composition (A2+, B2+) X2?.  相似文献   

15.
This work reports the application of thermodynamic models, including equations of state, to binary (salt-free) CH4-H2O fluid inclusions. A general method is presented to calculate the compositions of CH4-H2O inclusions using the phase volume fractions and dissolution temperatures of CH4 hydrate. To calculate the homogenization pressures and isolines of the CH4-H2O inclusions, an improved activity-fugacity model is developed to predict the vapor-liquid phase equilibrium. The phase equilibrium model can predict methane solubility in the liquid phase and water content in the vapor phase from 273 to 623 K and from 1 to 1000 bar (up to 2000 bar for the liquid phase), within or close to experimental uncertainties. Compared to reliable experimental phase equilibrium data, the average deviation of the water content in the vapor phase and methane solubility in the liquid phase is 4.29% and 3.63%, respectively. In the near-critical region, the predicted composition deviations increase to over 10%. The vapor-liquid phase equilibrium model together with the updated volumetric model of homogenous (single-phase) CH4-H2O fluid mixtures (Mao S., Duan Z., Hu J. and Zhang D. (2010) A model for single-phase PVTx properties of CO2-CH4-C2H6-N2-H2O-NaCl fluid mixtures from 273 to 1273 K and from 1 to 5000 bar. Chem. Geol.275, 148-160), is applied to calculate the isolines, homogenization pressures, homogenization volumes, and isochores at specified homogenization temperatures and compositions. Online calculation is on the website: http://www.geochem-model.org/.  相似文献   

16.
Interactions in a Fe–C–O–H–N system that controls the mobility of siderophile nitrogen and carbon in the Fe0-saturated upper mantle are investigated in experiments at 6.3–7.8 GPa and 1200–1400 °C. The results show that the γ-Fe and metal melt phases equilibrated with the fluid in a system unsaturated with carbon and nitrogen are stable at 1300 °C. The interactions of Fe3C with an N-rich fluid in a graphite-saturated system produce the ε-Fe3N phase (space group P63/mmc or P6322) at subsolidus conditions of 1200–1300 °C, while N-rich melts form at 1400 °C. At IW- and MMO-buffered hydrogen fugacity (fH2), fluids vary from NH3- to H2O-rich compositions (NH3/N2?>?1 in all cases) with relatively high contents of alkanes. The fluid derived from N-poor samples contains less H2O and more carbon which mainly reside in oxygenated hydrocarbons, i.e., alcohols and esters at MMO-buffered fH2 and carboxylic acids at unbuffered fH2 conditions. In unbuffered conditions, N2 is the principal nitrogen host (NH3/N2?≤?0.1) in the fluid equilibrated with the metal phase. Relatively C- and N-rich fluids in equilibrium with the metal phase (γ-Fe, melt, or Fe3N) are stable at the upper mantle pressures and temperatures. According to our estimates, the metal/fluid partition coefficient of nitrogen is higher than that of carbon. Thus, nitrogen has a greater affinity for iron than carbon. The general inference is that reduced fluids can successfully transport volatiles from the metal-saturated mantle to metal-free shallow mantle domains. However, nitrogen has a higher affinity for iron and selectively accumulates in the metal phase, while highly mobile carbon resides in the fluid phase. This may be a controlling mechanism of the deep carbon and nitrogen cycles.  相似文献   

17.
The equilibrium conditions of the following reaction 2 zoisite +1 CO2?3 anorthite+1 calcite+1 H2O 2 Ca2Al3[O/OH/SiO4/Si2O7]+1 CO2?3 CaAl2Si2O8+1 CaCO3+1 H2O have been determined experimentally at total pressures of P j= 2000 bars, P f =5000 bars, and P f =7000 bars. Owing to the vertical position of the equilibrium curves in isobaric T- \(X_{{\text{CO}}_{\text{2}} }\) diagrams, the composition of the binary H2O-CO2 fluid phase coexisting with zoisite is independent of temperature in the temperature interval investigated. According to our experiments, orthorhombic zoisite is only stable in equilibrium with a fluid phase at a concentration of CO2 which is less than, respectively, ca. 2 Mol% CO2 at P f =2000 bars, ea. 6 Mol% at P f =5000 bars, and ca. 10 Mol% at P f =7000 bars. Thus, the fluid phase coexisting with zoisite is rich in H2O. While this is independent of temperature the experimental data demonstrate that the influence of pressure cannot be neglected: With increasing pressure the concentration of CO2 of the fluid phase coexisting with zoisite can rise a little. The position of the reaction studied, which is independent of temperature and exhibits small values of \(X_{{\text{CO}}_{\text{2}} }\) ,leads to two important petrogenetic conclusions:
  1. The occurrence of zoisite is an indicator for a CO2-poor and H2O-rich fluid composition during metamorphism of marly calcsilicates.
  2. If the concentration of CO2 of the fluid phase coexisting with zoisite exceeds the equilibrium value of \(X_{{\text{CO}}_{\text{2}} }\) calcite+anorthite+H2O is formed from zoisite+CO2. Thus, a considerable increase in the anorthite-content of plagioelase is possible.
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18.
A H2O-NaCl-KCl-rich fluid occurs occasionally in fluid inclusions in a variety of geological environments. The properties of this fluid provide information about the conditions of entrapment, and thereby, conditions that have affected the rock. New purely empirical and thermodynamic models are developed in this study to reproduce the properties of the H2O-NaCl-KCl fluid system, especially the liquidus at variable pressures (the solid–liquid-vapour surface, i.e. SLV), and at constant pressures (the solid–liquid surface, i.e. SL). The SLV surface is modelled according to “best-fit” polynomial equations, which relate temperature, pressure and composition. The SL surfaces, at constants pressures, are modelled according to thermodynamic principles, i.e. the equality of chemical potentials of components (NaCl and KCl) in each phase at equilibrium. The models are valid up to 400?MPa and 900°C and can be applied to fluid inclusions studies to obtain salinities from dissolution temperatures of salt crystals. The new models are included in the program AqSo WHS that forms part of the software package FLUIDS (Bakker, Chem Geol 194:3–23, 2003), to be able to apply directly the mathematical functions in fluid inclusion studies and in general fluid properties investigations.  相似文献   

19.
Phase equilibria in the system H2O-NaCl have been determined to 1000°C and 1500 bars using synthetic fluid inclusions formed by healing fractures in inclusion-free Brazilian quartz in the presence of the two coexisting, immiscible H2O-NaCl fluids at various temperatures and pressures. Petrographic and microthermometric analyses indicate that the inclusions trapped one or the other of the two fluids present, or mixtures of the two. Salinities of the two coexisting phases were obtained from heating and freezing studies on those inclusions which trapped only a single, homogeneous fluid phase.Results of the present study are consistent with previously published data on the H2O-NaCl system at lower temperatures and pressures, and indicate that the two-phase field extends well into the P-T range of most shallow magmatic-hydrothermal activity. As a consequence, chloride brines exsolved from many epizonal plutons during the process of “second-boiling” should immediately separate into a high-salinity liquid phase and a lower salinity vapor phase and produce coexisting halite-bearing and vapor-rich fluid inclusions. This observation is consistent with results of numerous fluid inclusion studies of ore deposits associated with shallow intrusions, particularly the porphyry copper deposits, in which halite-bearing and coexisting vapor-rich inclusions are commonly associated with the earliest stages of magmatic-hydrothermal activity.  相似文献   

20.
The P-V-T-X properties of H2O-salt systems are compared depending on the solubility coefficient of compounds contained in these systems and the presence or absence of critical phenomena in the saturated solutions. Data on synthetic and natural inclusions captured in minerals at elevated temperatures and pressures and employed to discuss the principal features of phase diagrams of the H2O-NaCl system (type I) and H2O-NaF system (type II or P-Q type). It is demonstrated how characteristics of magmatic fluids of various types are manifested during the development of miarolitic pegmatites (Malkhan field in Transbaikalia) and during the crystallization of F-rich ongonitic melts (Ary-Bulak Massif in eastern Transbaikalia). Characteristics of solutions and gas-rich (gaseous) fluid inclusions in quartz phenocrysts from porphyritic ongonites (disappearance of the liquid regardless of its density and the overall salinity near the critical point of water, distinctive features of the dissolution of the crystalline phase, and the ability of the inclusions to withstand heating to 1400°C without decrepitation), and the richness of the fluid-magmatic system as a whole in F suggest that the ongonite melt crystallized in the presence of low-density NaF-bearing fluids of the P-Q type with a minor admixture of chlorides. It is important to identify the type of solutions in the fluid inclusions, because without knowing this type, it is impossible to accurately enough calculate the pressure at the temperatures of inclusion capture. For example, the unwarranted classification of solutions of type II (P-Q) in inclusions with the chloride system results in a significant overestimation of the calculated fluid pressures. A technique is proposed for studying the high-temperature immiscibility region in P-Q systems based on data obtained on gaseous fluid inclusions.  相似文献   

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