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1.
Deep saline aquifers in sedimentary basins are considered to have the greatest potential for CO2 geological storage in order to reduce carbon emissions. CO2 injected into a saline sandstone aquifer tends to migrate upwards toward the caprock because the density of the supercritical CO2 phase is lower than that of formation water. The accumulated CO2 in the upper portions of the reservoir gradually dissolves into brine, lowers pH and changes the aqueous complexation, whereby induces mineral alteration. In turn, the mineralogical composition could impose significant effects on the evolution of solution, further on the mineralized CO2. The high density of aqueous phase will then move downward due to gravity, give rise to “convective mixing,” which facilitate the transformation of CO2 from the supercritical phase to the aqueous phase and then to the solid phase. In order to determine the impacts of mineralogical compositions on trapping amounts in different mechanisms for CO2 geological storage, a 2D radial model was developed. The mineralogical composition for the base case was taken from a deep saline formation of the Ordos Basin, China. Three additional models with varying mineralogical compositions were carried out. Results indicate that the mineralogical composition had very obvious effects on different CO2 trapping mechanisms. Specific to our cases, the dissolution of chlorite provided Mg2+ and Fe2+ for the formation of secondary carbonate minerals (ankerite, siderite and magnesite). When chlorite was absent in the saline aquifer, the dominant secondary carbon sequestration mineral was dawsonite, and the amount of CO2 mineral trapping increased with an increase in the concentration of chlorite. After 3000 years, 69.08, 76.93, 83.52 and 87.24 % of the injected CO2 can be trapped in the solid (mineral) phase, 16.05, 11.86, 8.82 and 6.99 % in the aqueous phase, and 14.87, 11.21, 7.66 and 5.77 % in the gas phase for Case 1 through 4, respectively.  相似文献   

2.
Theory is derived from the work of Urey (Urey H. C. [1947] The thermodynamic properties of isotopic substances. J. Chem. Soc. 562-581) to calculate equilibrium constants commonly used in geochemical equilibrium and reaction-transport models for reactions of individual isotopic species. Urey showed that equilibrium constants of isotope exchange reactions for molecules that contain two or more atoms of the same element in equivalent positions are related to isotope fractionation factors by α = (Kex)1/n, where n is the number of atoms exchanged. This relation is extended to include species containing multiple isotopes, for example 13C16O18O and 1H2H18O. The equilibrium constants of the isotope exchange reactions can be expressed as ratios of individual isotope equilibrium constants for geochemical reactions. Knowledge of the equilibrium constant for the dominant isotopic species can then be used to calculate the individual isotope equilibrium constants.Individual isotope equilibrium constants are calculated for the reaction CO2g = CO2aq for all species that can be formed from 12C, 13C, 16O, and 18O; for the reaction between 12C18O2aq and 1H218Ol; and among the various 1H, 2H, 16O, and 18O species of H2O. This is a subset of a larger number of equilibrium constants calculated elsewhere (Thorstenson D. C. and Parkhurst D. L. [2002] Calculation of individual isotope equilibrium constants for implementation in geochemical models. Water-Resources Investigation Report 02-4172. U.S. Geological Survey). Activity coefficients, activity-concentration conventions for the isotopic variants of H2O in the solvent 1H216Ol, and salt effects on isotope fractionation have been included in the derivations. The effects of nonideality are small because of the chemical similarity of different isotopic species of the same molecule or ion. The temperature dependence of the individual isotope equilibrium constants can be calculated from the temperature dependence of the fractionation factors.The derivations can be extended to calculation of individual isotope equilibrium constants for ion pairs and equilibrium constants for isotopic species of other chemical elements. The individual isotope approach calculates the same phase isotopic compositions as existing methods, but also provides concentrations of individual species, which are needed in calculations of mass-dependent effects in transport processes. The equilibrium constants derived in this paper are used to calculate the example of gas-water equilibrium for CO2 in an acidic aqueous solution.  相似文献   

3.
A prognosis of the geochemical effects of CO2 storage induced by the injection of CO2 into geologic reservoirs or by CO2 leakage into the overlaying formations can be performed by numerical modelling (non-invasive) and field experiments. Until now the research has been focused on the geochemical processes of the CO2 reacting with the minerals of the storage formation, which mostly consists of quartzitic sandstones. Regarding the safety assessment the reactions between the CO2 and the overlaying formations in the case of a CO2 leakage are of equal importance as the reactions in the storage formation. In particular, limestone formations can react very sensitively to CO2 intrusion. The thermodynamic parameters necessary to model these reactions are not determined explicitly through experiments at the total range of temperature and pressure conditions and are thus extrapolated by the simulation code. The differences in the calculated results lead to different calcite and CO2 solubilities and can influence the safety issues.This uncertainty study is performed by comparing the computed results, applying the geochemical modelling software codes The Geochemist’s Workbench, EQ3/6, PHREEQC and FactSage/ChemApp and their thermodynamic databases. The input parameters (1) total concentration of the solution, (2) temperature and (3) fugacity are varied within typical values for CO2 reservoirs, overlaying formations and close-to-surface aquifers. The most sensitive input parameter in the system H2O–CO2–NaCl–CaCO3 for the calculated range of dissolved calcite and CO2 is the fugacity of CO2. Hence, the largest range of dissolved calcite is calculated at high fugacities and is 210 mmol/kgw. The average deviation of the results using the databases phreeqc.dat and wateq4f.dat in combination with the code PHREEQC is lowest in comparison to the results of the specific model of Duan and Li, which represents the experimental values at best. Still, the solubility of CO2 is overestimated in the formation water using these two databases. Therefore, the model results calculate a larger retention capacity, defined as the quantity of CO2 dissolved in the formation water, than the Duan and Li model would do.  相似文献   

4.
The lower Triassic/Bunter sandstone and lower Jurassic/Rhät formations of the Northern Germany sedimentary basin constitute feasible reservoirs for the storage of CO2 from combustion of fossil fuels or industrial production processes. This study presents analyses of geochemical interactions between CO2, formation fluid and rock of these potential reservoirs using geochemical modelling in order to assess the short and long term impact of CO2 sequestration. Batch equilibrium modelling was performed first for assessing the consistency of fluid and mineralogy field data and for identifying potential secondary minerals under the influence of injected CO2. Inclusion of reaction kinetics in the batch models allowed an observation of reaction paths and to estimate the time frame of geochemical reactions. Finally, one-dimensional equilibrium reactive transport modelling was used in order to investigate the direction of reactions under conditions of fluid flow and mass transport and to quantify feedbacks of reactions on transport processes.Results of the simulations performed show that dawsonite may act as the main CO2 storage mineral in both formations, while the carbonates calcite and dolomite dissolve over time. Also, changes in porosity and permeability are significant in the equilibrium reactive transport simulations. The time scale of kinetically controlled reactions observed in the kinetic batch modeling, however, suggests that CO2 mineral trapping in both formations requires very long time frames, and hence other mechanisms such as structural or solubility trapping seem to be more relevant within the injection or early post-injection phase for the studied formations.  相似文献   

5.
Miller field of the North Sea has had high concentrations of natural CO2 for ~70 Ma. It is an ideal analog for the long-term fate of CO2 during engineered storage, particularly for formation of carbonate minerals that permanently lock up CO2 in solid form. The Brae Formation reservoir sandstone contains an unusually high quantity of calcite concretions; however, C and O stable isotopic signatures suggest that these are not related to the present-day CO2 charge. Margins of the concretions are corroded, probably because of reduced pH due to CO2 influx. Dispersed calcite cements are also present, some of which postdate the CO2 charge and, therefore, are the products of mineral trapping. It is calculated that only a minority of the reservoired CO2 in Miller (6–24%) has been sequestrated in carbonates, even after 70 Ma of CO2 emplacement. Most of the CO2 accumulation is dissolved in pore fluids. Therefore, in a reservoir similar to the Brae Formation, engineered CO2 storage must rely on physical retention mechanisms because mineral trapping is both incomplete and slow.  相似文献   

6.
We conducted CO2–water–rock interaction experiments to elucidate the dissolution characteristics and geochemical trapping potential of three different altered andesitic to rhyolitic tuffaceous rocks (Tsugawa, Ushikiri and Daijima tuffaceous rock) relative to fresh mid-ocean ridge basalt. The experiments were performed under 1 MPa CO2 pressure to reproduce the water–rock–CO2 interactions in CO2 storage situations. Basalt showed high acid neutralization potential and rapid dissolution of silicate minerals. Two of the tuffaceous rocks (Ushikiri and Daijima) showed relatively high solubility trapping potential, mainly due to the dissolution of carbonate minerals in the andesitic Ushikiri tuffaceous rock and the ion-exchange reaction with zeolite minerals in the rhyolitic Daijima tuffaceous rock. The mineral trapping potential of the Ushikiri tuffaceous rock was found to be relatively high, due to the rapid dissolution of Mg- and Ca-bearing silicate minerals. Our experimental results suggest that regions of porous and andesitic tuffaceous rock hold global promise as CO2 storage sites.  相似文献   

7.
A sedimentary formation perturbated by supercritical CO2 reacts by dissolving primary minerals and forming new secondary phases. In this process CO2 may be trapped in stable carbonate minerals and may thereby be immobilized for long time spans. The potential for mineral trapping can be estimated by solving kinetic expressions for the reservoir minerals and possible secondary phases. This is, however, not trivial as kinetic data are uncertain or even lacking for the minerals of interest. Here, the rate equations most commonly used for CO2 storage simulations have been solved, and the rate parameters varied, to obtain sensitivity on the total amount of CO2 stored as mineral carbonate. As various expressions are in use to estimate growth rates of secondary carbonates, three formulations were compared, including one taking into account mineral nucleation preceding growth. The sensitivity studies were done on two systems, the Utsira Sand being representative for a cold quartz-rich sand (37 °C, 100 bar CO2), and the Gulf Coast Sediment, being representative for a medium temperature quartz–plagioclase-rich system (75 °C, 300 bar CO2).The simulations showed that the total predicted CO2 mineral storage is especially sensitive to the choice of growth rate model and the reactive surface area. The largest sensitivity was found on α, fraction of total surface area available for reactions, with a reduction of one order of magnitude for all reacting phases leading to 3–4 times lower predicted CO2 mineral storage. Because the reactive surface area is highly uncertain for natural systems, the range in predicted results may be even larger. The short-term predictions (<100–1000 a), such as the onset of carbonate growth, were highly sensitive to nucleation and growth rates. Moreover, the type of carbonate minerals formed was shown to be model dependent, with the simplest model predicting an unlikely carbonate assemblage at low temperature (i.e., formation of dolomite at 37 °C). Therefore, to use kinetic models to upscale short-term (<months) laboratory experiments in time, to identify the past reactions and physical conditions of natural CO2 storage analogues, and finally to predict the potential for CO2 trapping in existing and future storage projects, more knowledge has to be collected, especially on the reactive surface area of CO2 storage reservoirs, and on the rate of secondary carbonate nucleation and growth.  相似文献   

8.
Changes in magmatic assemblages and crystal stability as a response of CO2-flushing in basaltic systems have rarely been directly addressed experimentally, making the role of CO2 in magma dynamics still controversial and object of scientific debate. We conducted a series of experiments to understand the response of magmas from Etna volcano to CO2 flushing. We performed a first experiment at 300 MPa to synthesize a starting material composed of crystals of some hundreds of µm and melt pools. This material is representative of an initial magmatic assemblage composed of plagioclase, clinopyroxene and a water-undersaturated melt with 1.6 wt% H2O. In a second step, the initial assemblage was equilibrated at 300 and 100 MPa with fluids having different XCO 2 fl (CO2/(H2O + CO2)). At low XCO 2 fl (< 0.2 to 0.4), plagioclase is completely dissolved and clinopyroxene show dissolution textures. For relatively high XCO 2 fl (0.9 at 300 MPa), the flushing of a CO2-rich fluid phase leads to an increase of the amount of clinopyroxene and a decrease of the abundance of plagioclase at 300 MPa. This decrease of plagioclase proportion is associated with a change in An content. Our experiments demonstrate that flushing basaltic systems with fluids may drastically affect crystal textures and phase equilibria depending on proportions of H2O and CO2 in the fluid phase. Since texture and crystal proportions are among the most important parameters governing the rheology of magmas, fluid flushing will also influence magma ascent to the Earth’s surface. The experimental results open new perspectives to decipher the textural and compositional record of minerals observed in volcanic rocks from Mt. Etna, and at the same time offer the basis for interpreting the information preserved in minerals from other basaltic volcanoes erupting magmas enriched in CO2.  相似文献   

9.
The Neoproterozoic granite of Gabal Abu Diab, central Eastern Desert of Egypt, comprises mainly garnet-bearing granite and alkali feldspar granite intruded into calc-alkaline granodiorite–tonalite and metagabbro–diorite complexes. The garnet-bearing granite is composed mainly of plagioclase, K-feldspar, quartz, garnet and primary muscovite ± biotite. The presence of garnet and primary muscovite of Abu-Diab granite suggests its highly fractionated character. Geochemically, the garnet-bearing granite is highly fractionated as indicated from the high contents of SiO2 (74.85–77.5%), alkalis (8.27 to 9.2%, Na2O+K2O) and the trace elements association: Ga, Zn, Zr, Nb and Y. This granite is depleted in CaO, MgO, P2O5, Sr and Ba. The alumina saturation (Shand Index, molar ratio A/CNK) of 1.0 to 1.1 indicates the weak peraluminous nature of this garnet-bearing granite. The geochemical characteristics of the Abu Diab garnet-bearing granite are consistent with either the average I-type or A-type granite and also suggest post-orogenic or anorogenic setting. A fluid inclusions study reveals the presence of three fluid generations trapped into the studied granite. The earlier is a complex CO2–H2O fluid trapped in primary fluid inclusions with CO2 contents >?60 vol.%. These inclusions were probably trapped at minimum temperature >?400°C and minimum pressure >?2 kb. The second is immiscible water–CO2 fluid trapped in secondary and/or pseudo-secondary inclusions. The trapping conditions were estimated at temperature between 400°C and 170°C and pressure between 900 and 2000 bar. The latest fluid is low-salinity aqueous fluid trapped in secondary two-phase and mono-phase inclusions. The trapping conditions were estimated at temperature between 90°C and 160°C and pressure <?900 bar. The origin of the early fluid generation is magmatic fluid while the second and third fluids are of hydrothermal and meteoric origin, respectively.  相似文献   

10.
《Applied Geochemistry》2004,19(6):917-936
Carbon dioxide disposal into deep aquifers is a potential means whereby atmospheric emissions of greenhouse gases may be reduced. However, our knowledge of the geohydrology, geochemistry, geophysics, and geomechanics of CO2 disposal must be refined if this technology is to be implemented safely, efficiently, and predictably. As a prelude to a fully coupled treatment of physical and chemical effects of CO2 injection, the authors have analyzed the impact of CO2 immobilization through carbonate mineral precipitation. Batch reaction modeling of the geochemical evolution of 3 different aquifer mineral compositions in the presence of CO2 at high pressure were performed. The modeling considered the following important factors affecting CO2 sequestration: (1) the kinetics of chemical interactions between the host rock minerals and the aqueous phase, (2) CO2 solubility dependence on pressure, temperature and salinity of the system, and (3) redox processes that could be important in deep subsurface environments. The geochemical evolution under CO2 injection conditions was evaluated. In addition, changes in porosity were monitored during the simulations. Results indicate that CO2 sequestration by matrix minerals varies considerably with rock type. Under favorable conditions the amount of CO2 that may be sequestered by precipitation of secondary carbonates is comparable with and can be larger than the effect of CO2 dissolution in pore waters. The precipitation of ankerite and siderite is sensitive to the rate of reduction of Fe(III) mineral precursors such as goethite or glauconite. The accumulation of carbonates in the rock matrix leads to a considerable decrease in porosity. This in turn adversely affects permeability and fluid flow in the aquifer. The numerical experiments described here provide useful insight into sequestration mechanisms, and their controlling geochemical conditions and parameters.  相似文献   

11.
We use a reactive diffusion model to investigate what happens to CO2 injected into a subsurface sandstone reservoir capped by a chlorite- and illite-containing shale seal. The calculations simulate reaction and transport of supercritical (SC) CO2 at 348.15 K and 30 MPa up to 20,000 a. Given the low shale porosity (5%), chemical reactions mostly occurred in the sandstone for the first 2000 a with some precipitation at the ss/sh interface. From 2000 to 4000 a, ankerite, dolomite and illite began replacing Mg–Fe chlorite at the sandstone/shale interface. Transformation of chlorite to ankerite is the dominant reaction occluding the shale porosity in most simulations: from 4000 to 7500 a, this carbonation seals the reservoir and terminates reaction. Overall, the carbonates (calcite, ankerite, dolomite), chlorite and goethite all remain close to local chemical equilibrium with brine. Quartz is almost inert from the point of its dissolution/precipitation. However, the rate of quartz reaction controls the long-term decline in aqueous silica activity and its evolution toward equilibrium. The reactions of feldspars and clays depend strongly on their reaction rate constants (microcline is closer to local equilibrium than albite). The timing of porosity occlusion mostly therefore depends on the kinetic constants of kaolinite and illite. For example, an increase in the kaolinite kinetic constant by 0.25 logarithmic units hastened porosity closure by 4300 a. The earliest simulated closure of porosity occurred at approximately 108 a for simulations designed as sensitivity tests for the rate constants.These simulations also emphasize that the rate of CO2 immobilization as aqueous bicarbonate (solubility trapping) or as carbonate minerals (mineral trapping) in sandstone reservoirs depends upon reaction kinetics – but the relative fraction of each trapped CO2 species only depends upon the initial chemical composition of the host sandstone. For example, at the point of porosity occlusion the fraction of bicarbonate remaining in solution depends upon the initial Na and K content in the host rock but the fraction of carbonate mineralization depends only on the Ca, Mg, Fe content. Since ankerite is the dominant mineral that occludes porosity, the dissolved concentration of ferrous iron is also an important parameter. Future efforts should focus on cross-comparisons and ground-truthing of simulations made for standard case studies as well as laboratory measurements of the reactivities of clay minerals.  相似文献   

12.
Using chemical analyses and 25° pH measurements of quenched high-temperature waters, we calculate in situ pH and distribution of aqueous species at high temperature. This is accomplished by solving simultaneous mass action equations for complexes and redox equilibria and mass balance equations, on all components, including a H+ equation with as many as 60 terms (depending on water composition). This calculation provides accurate values for the activities of aqueous ions in a given water at high temperature, which are used to calculate an ion activity product (Q) for each of more than 100 minerals. The value of log(Q/K) for each mineral, where K is the equilibrium constant, provides a measure of proximity of the aqueous solution to equilibrium with the mineral. By plotting log Q/Kvs. T for natural waters, it is possible to determine: a) whether the water was in equilibrium with a host rock mineral assemblage, b) probable minerals in the equilibrium assemblage and c) the temperature of equilibrium. In cases where the fluid departs from equilibrium with a host rock assemblage, it is possible to determine whether this may result from boiling or dilution, and an estimate of amount of lost gas or diluting water can be determined.The calculation is illustrated by application to geothermal waters from Iceland, Broadlands, and Sulphur Bank, hot spring waters from Jemez, Yellowstone and Blackfoot Reservoir (Idaho) and fluid inclusions from the Sunnyside Mine, Colorado. It is shown that most geothermal waters approach equilibrium with a subsurface mineral assemblage at a temperature close to measured temperatures and that some hot springs also approach equilibrium with the host rock at temperatures above outlet temperatures but commonly below the Na-K-Ca temperatures. The log Q/K plots show that some discrepancies between Na-K-Ca temperatures on spring waters and actual temperatures result from a failure of alkali feldspars to equilibrate with the fluid and with each other.Calculations on Sulphur Bank fluids show that boiling probably caused cinnabar precipitation near 150°C and that the boiled fluids equilibrated with secondary minerals near 150° even though temperatures up to 185° have been measured at depth. For the fluid inclusions, the measured bubble temperatures are close to those calculated for equilibration of the fluid with the observed sulfide mineral assemblage.New estimates of stability constants for aluminum hydroxide complexes are included at the end of the paper.  相似文献   

13.
In this work 3-[2-(2-aminoethylamino)ethylamino]propyl trimethoxysilane (TRI) was employed to functionalize MWCNT containing hydroxyl groups (OH-MWCNT), and the XRD, FTIR, TGA and CHNS elemental analysis techniques were used to characterize the resulted adsorbents. The characterization results for amine-MWCNT showed amine groups effectively attached to the surface of the MWCNT. The equilibrium adsorption capacity of pure CO2 and CH4 and their binary mixture on the pristine MWCNT, OH-MWCNT and amine-MWCNT was measured through a set of equilibrium adsorption experiments at 303.2 and 318.2 K. Capacities of all three types of adsorbents for CO2 adsorption were higher than those for methane adsorption. Also, amine-MWCNT demonstrated better performance on CO2 adsorption than the other two adsorbents, especially at low partial pressures. The capacity of amine-MWCNT for pure CO2 adsorption was 2.5 and 4 times as much as those for pristine MWCNT and OH-MWCNT, respectively, at the temperature of 303.2 K and the pressure of 0.2 bar. The binary adsorption experiment revealed that CO2/CH4 selectivity for pristine MWCNT and amine-MWCNT in all molar fractions of CO2 is about 1.77 and 7, respectively.  相似文献   

14.
We have performed experiments to determine the effects of pressure, temperature and oxygen fugacity on the CO2 contents in nominally anhydrous andesitic melts at graphite saturation. The andesite composition was specifically chosen to match a low-degree partial melt composition that is generated from MORB-like eclogite in the convective, oceanic upper mantle. Experiments were performed at 1–3 GPa, 1375–1550?°C, and fO2 of FMQ ?3.2 to FMQ ?2.3 and the resulting experimental glasses were analyzed for CO2 and H2O contents using FTIR and SIMS. Experimental results were used to develop a thermodynamic model to predict CO2 content of nominally anhydrous andesitic melts at graphite saturation. Fitting of experimental data returned thermodynamic parameters for dissolution of CO2 as molecular CO2: ln(K 0) = ?21.79?±?0.04, ΔV 0?=?32.91?±?0.65 cm3mol?1, ΔH 0?=?107?±?21 kJ mol?1, and dissolution of CO2 as CO3 2?: ln(K 0 ) = ?21.38?±?0.08, ΔV 0?=?30.66?±?1.33 cm3 mol?1, ΔH 0?=?42?±?37 kJ mol?1, where K 0 is the equilibrium constant at some reference pressure and temperature, ΔV 0 is the volume change of reaction, and ΔH 0 is the enthalpy change of reaction. The thermodynamic model was used along with trace element partition coefficients to calculate the CO2 contents and CO2/Nb ratios resulting from the mixing of a depleted MORB and the partial melt of a graphite-saturated eclogite. Comparison with natural MORB and OIB data suggests that the CO2 contents and CO2/Nb ratios of CO2-enriched oceanic basalts cannot be produced by mixing with partial melts of graphite-saturated eclogite. Instead, they must be produced by melting of a source containing carbonate. This result places a lower bound on the oxygen fugacity for the source region of these CO2-enriched basalts, and suggests that fO2 measurements made on cratonic xenoliths may not be applicable to the convecting upper mantle. CO2-depleted basalts, on the other hand, are consistent with mixing between depleted MORB and partial melts of a graphite-saturated eclogite. Furthermore, calculations suggest that eclogite can remain saturated in graphite in the convecting upper mantle, acting as a reservoir for C.  相似文献   

15.
In peridotites, olivine, clinopyroxene, and orthopyroxene are complex solid solutions with wide stability fields. Depending mostly on bulk composition and pressure, these minerals may be accompanied by plagioclase (low pressure), spinel (moderate pressure), or garnet (high pressure), resulting in 4-phase and rarer 5-phase assemblages. Although a particular mineral assemblage is stable over a range of P–T, the compositions of the individual minerals vary with changing P–T conditions. Application of standard geothermobarometers to olivine–clinopyroxene–orthopyroxene–spinel peridotites is problematic. An alternative approach is to use a bulk rock composition to calculate equilibrium phase diagrams to determine the conditions under which a particular assemblage is stable. This requires consideration of the 7-component system SiO2–Al2O3–Cr2O3–FeO–MgO–CaO–Na2O, internally consistent thermodynamic data for end members, and reliable mixing models for all mineral solutions. Experimental studies in simpler systems, and solution models from the literature, permit derivation of multicomponent thermodynamic mixing models for the key minerals. The models, when applied to xenoliths from Kilbourne Hole, constrain P and T of equilibration and are less sensitive to mineral compositional variations, or uncertainty in activity models, than standard thermobarometry. Our modeling provides the first tightly constrained pressure estimates for Kilbourne Hole, placing the xenoliths in the spinel stability field at depths (30–45 km) that correspond to the uppermost mantle beneath the Rio Grande Rift. The fine-grained equigranular lherzolite, porphyroclastic lherzolite, and some harzburgite-dunite specimens equilibrated at average conditions of 11.5 Kbar-930°C, 12 Kbar-990°C, and 13 Kbar-1,080°C, respectively. The mantle beneath the Rio Grande Rift is layered; the fine-grained equigranular lherzolite derives from relatively shallow depth (35 km average), and the porphyroclastic lherzolite from slightly deeper levels. Lying 5–10 km beneath both lherzolites, the harzburgite-dunite represents a depth where melt extraction has significantly altered mantle chemistry and where local thermodynamic equilibrium has not been maintained.  相似文献   

16.
This study focused on the target injection layers of deep saline aquifers in the Shiqianfeng Fm. in the Carbon Capture and Sequestration (CCS) Demonstration Projects in the Ordos Basin, northwestern China. The study employed a combination method of experiments and numerical simulation to investigate the dissolution mechanism and impact factors of CO2 in these saline aquifers. The results showed (1) CO2 solubility in different types of water chemistry were shown in ascending order: MgCl2-type water < CaCl2-type water < Na2SO4-type water < NaCl-type water < Na2CO3-type water < distilled water. These results were consistent with the calculated results undertaken by TOUGHREACT with about 5% margin of error. CO2 solubility of Shiqianfeng Fm. saline was 1.05 mol/L; (2) compared with distilled water, the more complex the water’s chemical composition, the greater the increase in HCO3 ?concentration. While the water’s composition was relatively simple, the tested water’s HCO3 ?concentrations were in close accord with the calculated value undertaken by the TOUGHREACT code, and the more complex the water’s composition, the poorer the agreement was, probably due to the complex and unstable HCO3 ? complicating matters when in an aqueous solution system including both tested HCO3 ?concentration and calculated HCO3 ?concentration; (3) the CO2 solubility in the saline at the temperature conditions of 55 °C and 70 °C were 1.17 and 1.02 mol/L. When compared with the calculated value of 1.20 and 1.05 mol/L, they were almost the same with only 1 and 3% margin of error; concentrations of HCO3 ? were 402.73 mg/L (0.007 mol/L) and 385.65 mg/L (0.006 mol/L), while the simulation results were 132.16 mg/L (0.002 mol/L) and 128.52 mg/L (0.002 mol/L). From the contrast between the tested data and the calculated data undertaken by the TOUGHREACT code, it was shown that TOUGHRACT code could better simulate the interaction between saline and CO2 in the dissolution sequestration capacity. Therefore, TOUGHREACT code could be used for the inter-process prediction of CO2 long-term geological storage of CO2; (4) The Ca2+ concentration and SO4 2?concentration in saline water had less effect on the solubility of CO2 and HCO3 ?concentration. In addition, TDS and pH values of saline affected not only the solubility of CO2, but also the conversion of CO2 to HCO3 ? due to that they can affect the activity and acid-base balance. So in fact, we just need to consider that the TDS and pH values are main impact factors in the dissolution sequestration capacity of CO2 geological sequestration in deep saline aquifers.  相似文献   

17.
A microthermometric study of inclusions in granites and pegmatites in the Proterozoic Harney Peak Granite system identified four types of inclusions. Type 1 inclusions are mixtures of CO2 and H2O and have low salinities, on average 3.5 wt.% NaCleq; type 2 inclusions are aqueous solutions of variable salinities, from 0 to 40% wt.% NaCleq; type 3 inclusions are carbonic, dominated by CO2, with no detectable water; and type 4 inclusions consist of 20 to 100% solids, with the remaining volume occupied by a CO2-H2O fluid. Many inclusions have a secondary character; however, a primary character can be unambiguously established in several occurrences of the type 1 inclusions. These inclusions were trapped above the solidus and represent the exsolved magmatic fluid. The secondary populations of types 1, 2, and 3 probably formed as a result of reequilibration and unmixing of the type 1 fluid that progressively changed composition and density with decreasing temperature and pressure and was finally trapped along healed microfractures under subsolidus conditions. Type 4 inclusions are primary and are interpreted to be trapped, fluid-bearing, complex silicate melts that subsequently solidified or underwent other posttrapping changes.It is demonstrated that primary type 1 fluid inclusions that coexist with crystallized melt inclusions in the complex, Li-bearing Tin Mountain pegmatite were trapped along the two-fluid phase boundary in the system CO2-H2O-NaCleq. Consequently, the temperature and pressure conditions of trapping are identical to the bulk homogenization conditions—on average 340°C and 2.7 kbar. These conditions indicate that this Li-, Cs-, Rb-, P-, and B-rich pegmatite crystallized at some of the lowest known temperatures for a silicate melt in the crust. An internally consistent, empirical solvus surface in P-T-XCO2 coordinates was generated for the pseudobinary CO2-(H2O-4.3 wt.% NaCleq) pegmatite fluid system. Distribution coefficients for the major species CO2, H2O, NaCl, and CH4 between the immiscible CO2-rich and H2O-rich fluid phases as a function of pressure and temperature were extracted from data for the two cogenetic fluid inclusions types.  相似文献   

18.
Thermodynamic properties for aqueous alkyl sulfides have been compiled and/or estimated through established methods. These properties are used to investigate reactions among various sulfur compounds in a variety of geological environments, ranging from sea floor hydrothermal systems to organic-rich sludge. Using thermodynamic data and the revised Helgeson-Kirkham-Flowers (HKF) equations of state, along with geochemical constraints imposed by the environment, it is possible to estimate the abiotic production of this class of organic sulfur compounds. For example, in hydrothermal systems in which H2 and H2S concentrations are buffered by the pyrite–pyrrhotite–magnetite (PPM) mineral assemblage, calculated equilibrium activities of dimethyl sulfide (DMS) are as high as 10−3 through formation reactions in which the environment contains millimolal concentrations of CO2. Higher activities are obtained when DMS formation from CO is considered and when more reducing mineral assemblages are present.  相似文献   

19.
Early Archean (3.46 Ga) hydrothermally altered basaltic rocks exposed near Marble Bar, eastern Pilbara Craton, have been studied in order to reveal geological and geochemical natures of seafloor hydrothermal carbonatization and to estimate the CO2 flux sunk into the altered oceanic crust by the carbonatization. The basaltic rocks are divided into basalt and dolerite, and the basalt is further subdivided into type I, having original igneous rock textures, and type II, lacking these textures due to strong hydrothermal alteration. Primary clinopyroxene phenocrysts are preserved in some part of the dolerite samples, and the alteration mineral assemblage of dolerite (chlorite + epidote + albite + quartz ± actinolite) indicates that the alteration condition was typical greenschist facies. In other samples, all primary minerals were completely replaced by secondary minerals, and the alteration mineral assemblage of the type I and type II basalts (chlorite + K-mica + quartz + carbonate minerals ± albite) is characterized by the presence of K-mica and carbonate minerals and the absence of Ca-Al silicate minerals such as epidote and actinolite, suggesting the alteration condition of high CO2 fugacity. The difference of the alteration mineral assemblages between basalt and dolerite is probably attributed to the difference of water/rock ratio that, in turn, depends on their porosity.Carbonate minerals in the carbonatized basalt include calcite, ankerite, and siderite, but calcite is quite dominant. The δ13C values of the carbonate minerals are −0.3 ± 1.2‰ and mostly within the range of marine carbonate, indicating that the carbonate minerals were formed by seafloor hydrothermal alteration and that carbonate carbon in the altered basalt was derived from seawater. Whole-rock chemical composition of the basaltic rocks is essentially similar to that of modern mid-ocean ridge basalt (MORB) except for highly mobile elements such as K2O, Rb, Sr, and Ba. Compared to the least altered dolerite, all altered basalt samples are enriched in K2O, Rb, and Ba, and are depleted in Na2O, reflecting the presence of K-mica replacing primary plagioclase. In addition, noticeable CO2 enrichment is recognized in the basalt due to the ubiquitous presence of carbonate minerals, but there was essentially neither gain nor loss of CaO. This suggests that the CO2 in the hydrothermal fluid (seawater) was trapped by using Ca originally contained in the basalt. The CaO/CO2 ratios of the basalt are generally the same as that of pure calcite, indicating that Ca in the basalt was almost completely converted to calcite during the carbonatization, although Mg and Fe were mainly redistributed into noncarbonate minerals such as chlorite.The carbon flux into the Early Archean oceanic crust by the seafloor hydrothermal carbonatization is estimated to be 3.8 × 1013 mol/yr, based on the average carbon content of altered oceanic crust of 1.4 × 10-3 mol/g, the alteration depth of 500 m, and the spreading rate of 1.8 × 1011 cm2/yr. This flux is equivalent to or greater than the present-day total carbon flux. It is most likely that the seafloor hydrothermal carbonatization played an important role as a sink of atmospheric and oceanic CO2 in the Early Archean.  相似文献   

20.
The phase equilibrium and growth of mixed (Ba,Pb)(NO3)2 crystals in aqueous solutions were investigated. The microcrystallization method was adapted to systems with isomorphic components, where crystal composition deviates from the thermodynamic equilibrium even at a low supercooling. The solid phase is characterized by continuous miscibility of the components within the analyzed ranges of temperature and solution composition. The diagram is characterized by substantial nonlinearity of the solubility isotherms and nonuniformity of the solid isocomposite location. Quasiequilibrium paths change their slope depending on solution enrichment in Ba(NO3)2 and depletion in Pb(NO3)2. The area of curvature of quasiequilibrium paths is coordinated with the area of the changing isotherm slope, i.e., the area of “remarkable” points, where the behavior of the system changes drastically. Examples of theoretical zoning of a crystal approximated to a sphere were calculated for paths at a temperature decreasing from 50 to 15°C. The content of the Ba component decreases toward the periphery with the consecutive overgrowing of zones. Each zone corresponds to one gram of (Ba,Pb)(NO3)2. Crystals grown from different initial solutions consist of different numbers of zones owing to the nonlinearity of solubility isotherms. Specific features of mixed crystal formation should be taken into account in genetic interpretation of natural minerals of mixed composition.  相似文献   

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