The dissolution of calcite in CO2-saturated solutions at 25°C and 1 atmosphere total pressure

The dissolution of Iceland spar in CO₂-saturated solutions at 25°C and 1 atm total pressure has been followed by measurement of pH as a function of time. Surface concentrations of reactant and product species have been calculated from bulk fluid data using mass transport theory and a model that accounts for homogeneous reactions in the bulk fluid. The surface concentrations are found to be close to bulk solution values. This indicates that calcite dissolution under the experimental conditions is controlled by the kinetics of surface reaction. The rate of calcite dissolution follows an empirical second order relation with respect to calcium and hydrogen ion from near the initial condition (pH 3.91) to approximately pH 5.9. Beyond pH 5.9 the rate of surface reaction is greatly reduced and higher reaction orders are observed. Calculations show that the rate of calcite dissolution in natural environments may be influenced by both transport and surface-reaction processes. In the absence of inhibition, relatively short times should be sufficient to establish equilibrium.     

Investigation of CO2 behavior and study on design of optimal injection into Gorae-V aquifer

This study presents the Bottom-hole pressure (BHP) behavior with different wettabilities and the optimal design scheme to effectively inject CO₂ into the Gorae-V aquifer. As a result, the injection rate and injectivity were increased as the wettability condition became more water-wet. However, the more wettability condition becomes water-wet, the more the ultimate CO₂ injection volume decreases. When the injectivity was 346 ton/day/Mpa at the Gorae-V aquifer, the aquifer can sustain CO₂ injection at a rate of 2,425 tons per day over this time period. A design for a complete CCS system was developed based on the existing off-shore pipeline in combination with new on-shore CO₂ transport infrastructure, and a pressure of 12.8 MPa is required at the CO₂ source to maintain this injection rate.     

Review of the systematics of CO2–H2O fluid inclusions

Aqueous solutions that contain volatile (gas) components are one of the most important types of fluid in the Earth's crust. The record that such fluids have left in the form of fluid inclusions in minerals provides a wealth of insight into the geochemical and petrologic processes in which the fluids participated. This article reviews the systematics of CO₂–H₂O fluid inclusions as a starting point for interpreting the chemically more complex systems. The phase relations of the binary are described with respect to a qualitative P–T–X model, and isoplethic–isochoric paths through this model are used to explain the equilibrium and non-equilibrium behaviour of fluid inclusions during microthermometric heating and cooling. The P–T–X framework is then used to discuss the various modes of fluid inclusion entrapment, and how the resulting assemblage textures can be used to interpret the P–T conditions, phase states, and evolution paths of the parent solutions. Finally, quantitative methods are reviewed by which bulk molar volume and composition of CO₂–H₂O fluid inclusions can be determined from microthermometric observations of phase transitions.     

超临界CO2注入煤层对顶板岩石纵波速度及力学响应特征研究

深部煤层CO₂地质封存与CH₄强化开采(CO₂–ECBM)技术在提高煤层气采收率的同时可实现碳减排,具有能源和环境双重效益。超临界CO₂(ScCO₂)、水和煤层顶板之间的地球化学反应可改变其物理力学性质,增加CO₂泄漏的风险。以沁水盆地胡底煤矿3号煤层顶板岩石为研究对象,开展“ScCO₂–水–岩”地球化学反应模拟实验,探讨CO₂煤层封存条件下ScCO₂–水–顶板岩样地球化学反应过程及其对岩石纵波速度和力学性质的影响。结果表明:ScCO₂–水–岩之间化学溶蚀反应造成岩样Ca、Mg元素显著降低,促使岩样表面形成孤立状溶蚀孔,并随着反应时间的持续,进而形成大量的“溶蚀坑”和“溶蚀缝”;增加了岩样结构不连续性,使得声波传播路径增大、能量损失加剧,导致纵波波速降低;ScCO₂–水–岩反应后岩样的峰值强度和弹性模量降低,泊松比升高,且三者之间的变化率与反应时间之间呈现Logistic函数的变化关系。对于胡底煤矿而言,ScCO₂–水–岩反应过程中顶板力学性质的弱化不足以造成盖层的破裂和CO₂泄漏,但在评价煤层CO₂封存安全性时,还应考虑煤层吸附膨胀应力对顶板的影响。      

Melting relationships in the systems CaOCO2 and MgOCO2 to 33 kilobars

The melting temperatures of calcite and magnesite in the presence of excess CO₂ have been measured using Ag₂C₂O₄ in sealed capsules m a piston-cylinder apparatus. At 27 kbar, 11.5 wt % CO₂ dissolves in molten CaCO₂, depressing the freezing temperature from 1610 to 1505°C; and 6.5 wt % CO₂ dissolves in molten MgCO₃, depressing the freezing temperature from 1590 to 1510°C. The eutectic between calcite and lime was located at 1385°C at 27 kbar. These and other new results, combined with previously published data, permit completion of PT diagrams for the systems CaO-CO₂ and MgO-CO₂ from 1 bar to 35 kbar. The dissociation curve for each carbonate terminates at an invariant point where melting begins, at 40 bars and 1230°C for CaO-CO₂ and 23 kbar and 1550°C for MgO-CO₂ The differences between the two systems are explained by the different solubilities of CO₂ in the invariant liquids consequent upon the large pressure difference between the locations of these two invariant points. The results show that the temperatures for the beginning of melting of carbonates in the asthenosphere are lowered by about 100°C in the presence of CO₂.     

Oxygen isotope exchange between H2O and CO2 at elevated CO2 pressures: Implications for monitoring of geological CO2 storage

Traditionally, the application of stable isotopes in Carbon Capture and Storage (CCS) projects has focused on δ¹³C values of CO₂ to trace the migration of injected CO₂ in the subsurface. More recently the use of δ¹⁸O values of both CO₂ and reservoir fluids has been proposed as a method for quantifying in situ CO₂ reservoir saturations due to O isotope exchange between CO₂ and H₂O and subsequent changes in δ¹⁸O_H2O values in the presence of high concentrations of CO₂. To verify that O isotope exchange between CO₂ and H₂O reaches equilibrium within days, and that δ¹⁸O_H2O values indeed change predictably due to the presence of CO₂, a laboratory study was conducted during which the isotope composition of H₂O, CO₂, and dissolved inorganic C (DIC) was determined at representative reservoir conditions (50 °C and up to 19 MPa) and varying CO₂ pressures. Conditions typical for the Pembina Cardium CO₂ Monitoring Pilot in Alberta (Canada) were chosen for the experiments. Results obtained showed that δ¹⁸O values of CO₂ were on average 36.4 ± 2.2‰ (1σ, n = 15) higher than those of water at all pressures up to and including reservoir pressure (19 MPa), in excellent agreement with the theoretically predicted isotope enrichment factor of 35.5‰ for the experimental temperatures of 50 °C. By using ¹⁸O enriched water for the experiments it was demonstrated that changes in the δ¹⁸O values of water were predictably related to the fraction of O in the system sourced from CO₂ in excellent agreement with theoretical predictions. Since the fraction of O sourced from CO₂ is related to the total volumetric saturation of CO₂ and water as a fraction of the total volume of the system, it is concluded that changes in δ¹⁸O values of reservoir fluids can be used to calculate reservoir saturations of CO₂ in CCS settings given that the δ¹⁸O values of CO₂ and water are sufficiently distinct.     

CO2-poor composition of the fluid attending Franciscan and Sanbagawa low-grade metamorphism

Previous phase equilibrium and oxygen isotopic researches on the high-pressure, low-temperature metamorphic rocks of the Franciscan and Sanbagawa blueschist type terranes have demonstrated the near ubiquity of a fluid at high (≈ total) pressure and its oxygen-rich nature during metamorphism. The coexistence of quartz with a CaCO₃ polymorph instead of wollastonite, and of sphene rather than rutile + quartz + calcium carbonate in these rocks places narrow, rather low limits on the partial pressures of CO₂, as computed in this note; equilibrium calculations indicate that the mole fraction of carbon dioxide in the fluid must have been less than about 0.04 in the Sanbagawa terrane and less than 0.01 in the Franciscan terrane. The rocks are not sulfated or strongly oxidized, hence the only other likely component which could comprise the balance of this phase is H₂O. Evidently metamorphism in the Sanbagawa belt and particularly in the Franciscan terrane must have taken place in the presence of a highly aqueous fluid.     

火山岩吸附CO2气的成藏潜力及实例分析

火山岩的脱气实验和对昌德东CO2气藏气源的分析结果表明加热火山岩到250℃时,脱出挥发分总量为0.0299～0.0790mL/g,其中CO2脱出量为0.0218～0.0706mL/g(0.429～1.387wt%);挥发组分以CO2为主,还含有H2、CO、CH4等还原性气体,以及少量低碳烷烃,CO2含量和总烃呈现反比关系;基性岩的CO2脱出量、脱出率高于中、酸性岩;CO2脱出量与岩石碱质含量正相关.松辽盆地北部昌德东CO2气藏成藏模式为"自生自储",成藏CO2气主要来自深部被火山岩吸附的气.随岩浆上升,在岩浆冷凝成火山岩的过程中被吸附于火山岩的节理、劈理和晶体位错之中的CO2气,连同火山岩包体中的残留气,成为高纯CO2气藏的主要补给源,并非地幔气体沿大断裂上来直接充注成藏.     

A physicochemical framework for interpreting the biological calcification response to CO2-induced ocean acidification

A generalized physicochemical model of the response of marine organisms’ calcifying fluids to CO₂-induced ocean acidification is proposed. The model is based upon the hypothesis that some marine calcifiers induce calcification by elevating pH, and thus Ω_A, of their calcifying fluid by removing protons (H⁺). The model is explored through two end-member scenarios: one in which a fixed number of H⁺ is removed from the calcifying fluid, regardless of atmospheric pCO₂, and another in which a fixed external-internal H⁺ ratio ([H⁺]_E/[H⁺]_I) is maintained. The model is able to generate the full range of calcification response patterns observed in prior ocean acidification experiments and is consistent with the assertion that organisms’ calcification response to ocean acidification is more negative for marine calcifiers that exert weaker control over their calcifying fluid pH. The model is empirically evaluated for the temperate scleractinian coral Astrangia poculata with in situ pH microelectrode measurements of the coral’s calcifying fluid under control and acidified conditions. These measurements reveal that (1) the pH of the coral’s calcifying fluid is substantially elevated relative to its external seawater under both control and acidified conditions, (2) the coral’s [H⁺]_E/[H⁺]_I is approximately the same under control and acidified conditions, and (3) the coral removes fewer H⁺ from its calcifying fluid under acidified conditions than under control conditions. Thus, the carbonate system dynamics of A. poculata’s calcifying fluid appear to be most consistent with the fixed [H⁺]_E/[H⁺]_I end-member scenario. Similar microelectrode experiments performed on additional taxa are required to assess the model’s general applicability.     

阿勒泰恰夏铜矿床的富CO2流体与矿床成因

恰夏铜矿床位于新疆阿尔泰山南缘克兰火山-沉积盆地内,赋矿地层主要为下泥盆统康布铁堡组上亚组变质岩系.脉状铜矿化主要特征为:早期顺层石英脉,呈脉状或透镜状沿变质片理分布,有星点状黄铁矿产出;晚期含铜黄铁矿-石英脉,斜切变质围岩,黄铜矿以浸染状分布于石英脉裂隙中.石英脉中流体包裹体主要为富CO2包裹体,其次为水溶液包裹体,同时含有少量的碳质流体包裹体.显微测温研究表明,早期顺层石英中原生富CO2流体包裹体,CO2三相点温度(tm,CO2)集中在-61.5～-57.5℃,CO2部分均一温度(th,CO2)集中在25～27℃,完全均一温度(th,tot)集中于223～280℃,流体密度为0.82～0.90 g/cm3;含铜黄铁矿-石英脉中原生富CO2包裹体的tm,CO2集中于-61.5～-58.7℃,th,CO2集中在23.5～28.7℃,th,tot集中在230 ～ 310℃,流体密度0.81～0.86 g/cm3.成矿流体为中高温、中低盐度、富CO2的CO2-H2O-NaCl±CH4±N2体系.恰夏铜矿脉状铜矿化的成矿流体特征与造山型金矿床的流体包裹体特征类似,结合矿床产出的地质背景、控矿构造特征,认为脉状铜矿化的成因与造山-变质热液有关,是阿尔泰山南缘晚泥盆世一二叠纪造山-变质作用的产物.SRXRF测试富CO2流体包裹体中金属微量元素,显示其富集Au,可能表明富CO2流体对金的富集起到一定作用.     

CO2-water-basalt interaction. Numerical simulation of low temperature CO2 sequestration into basalts

The interaction between CO₂-rich waters and basaltic glass was studied using reaction path modeling in order to get insight into the water-rock reaction process including secondary mineral composition, water chemistry and mass transfer as a function of CO₂ concentration and reaction progress (ξ). The calculations were carried out at 25-90 °C and pCO₂ to 30 bars and the results were compared to recent experimental observations and natural systems. A thermodynamic dataset was compiled from 25 to 300 °C in order to simulate mineral saturations relevant to basalt alteration in CO₂-rich environment including revised key aqueous species for mineral dissolution reactions and apparent Gibbs energies for clay and carbonate solid solutions observed to form in nature. The dissolution of basaltic glass in CO₂-rich waters was found to be incongruent with the overall water composition and secondary mineral formation depending on reaction progress and pH. Under mildly acid conditions in CO₂ enriched waters (pH <6.5), SiO₂ and simple Al-Si minerals, Ca-Mg-Fe smectites and Ca-Mg-Fe carbonates predominated. Iron, Al and Si were immobile whereas the Mg and Ca mobility depended on the mass of carbonate formed and water pH. Upon quantitative CO₂ mineralization, the pH increased to >8 resulting in Ca-Mg-Fe smectite, zeolites and calcite formation, reducing the mobility of most dissolved elements. The dominant factor determining the reaction path of basalt alteration and the associated element mobility was the pH of the water. In turn, the pH value was determined by the concentration of CO₂ and extent of reaction. The composition of the carbonates depended on the mobility of Ca, Mg and Fe. At pH <6.5, Fe was in the ferrous oxidation state resulting in the formation of Fe-rich carbonates with the incorporation of Ca and Mg. At pH >8, the mobility of Fe and Mg was limited due to the formation of clays whereas Ca was incorporated into calcite, zeolites and clays. Competing reactions between clays (Ca-Fe smectites) and carbonates at low pH, and zeolites and clays (Mg-Fe smectites) and carbonates at high pH, controlled the availability of Ca, Mg and Fe, playing a key role for low temperature CO₂ mineralization and sequestration into basalts. Several problems of the present model point to the need of improvement in future work. The determinant factors linking time to low temperature reaction path modeling may not only be controlled by the primary dissolving phase, which presents challenges concerning non-stoichiometric dissolution, the leached layer model and reactive surface area, but may include secondary mineral precipitation kinetics as rate limiting step for specific reactions such as retrieved from the present reaction path study.     

四川冕宁木落稀土矿床稀土矿物中富CO2和H2流体包裹体研究

木落稀土矿床位于四川省冕宁县境内，其成矿与喜山期岩浆碳酸岩有关。通过对矿床中主要稀土矿物氟碳铈矿中流体包裹体的岩相学、包裹体显微测温分析和包裹体成分的LRM分析等，对成矿流体的特征、演化及稀土矿化过程进行了讨论，结果表明与稀土成矿有关的流体为富CO₂和SO₂ 的中高温、高压超临界流体。温度、压力降低和流体不混溶是造成稀土矿物沉淀的主要机制。     

CO2 solubility in dacitic melts equilibrated with H2O-CO2 fluids: Implications for modeling the solubility of CO2 in silicic melts

The solubility of CO₂ in dacitic melts equilibrated with H₂O-CO₂ fluids was experimentally investigated at 1250°C and 100 to 500 MPa. CO₂ is dissolved in dacitic glasses as molecular CO₂ and carbonate. The quantification of total CO₂ in the glasses by mid-infrared (MIR) spectroscopy is difficult because the weak carbonate bands at 1430 and 1530 cm⁻¹ can not be reliably separated from background features in the spectra. Furthermore, the ratio of CO_2,mol/carbonate in the quenched glasses strongly decreases with increasing water content. Due to the difficulties in quantifying CO₂ species concentrations from the MIR spectra we have measured total CO₂ contents of dacitic glasses by secondary ion mass spectrometry (SIMS).At all pressures, the dependence of CO₂ solubility in dacitic melts on x^fluid_CO2,total shows a strong positive deviation from linearity with almost constant CO₂ solubility at x_CO2fluid > 0.8 (maximum CO₂ solubility of 795 ± 41, 1376 ± 73 and 2949 ± 166 ppm at 100, 200 and 500 MPa, respectively), indicating that dissolved water strongly enhances the solubility of CO₂. A similar nonlinear variation of CO₂ solubility with x_CO2fluid has been observed for rhyolitic melts in which carbon dioxide is incorporated exclusively as molecular CO₂ (Tamic et al., 2001). We infer that water species in the melt do not only stabilize carbonate groups as has been suggested earlier but also CO₂ molecules.A thermodynamic model describing the dependence of the CO₂ solubility in hydrous rhyolitic and dacitic melts on T, P, f_CO2 and the mol fraction of water in the melt (x_water) has been developed. An exponential variation of the equilibrium constant K₁ with x_water is proposed to account for the nonlinear dependence of x_CO2,totalmelt on x_CO2fluid. The model reproduces the CO₂ solubility data for dacitic melts within ±14% relative and the data for rhyolitic melts within 10% relative in the pressure range 100-500 MPa (except for six outliers at low x_CO2fluid). Data obtained for rhyolitic melts at 75 MPa and 850°C show a stronger deviation from the model, suggesting a change in the solubility behavior of CO₂ at low pressures (a Henrian behavior of the CO₂ solubility is observed at low pressure and low H₂O concentrations in the melt). We recommend to use our model only in the pressure range 100-500 MPa and in the x_CO2fluid range 0.1-0.95. The thermodynamic modeling indicates that the partial molar volume of total CO₂ is much lower in rhyolitic melts (31.7 cm³/mol) than in dacitic melts (46.6 cm³/mol). The dissolution enthalpy for CO₂ in hydrous rhyolitic melts was found to be negligible. This result suggests that temperature is of minor importance for CO₂ solubility in silicic melts.     

A pedogenic goethite record of soil CO2 variations as a response to soil moisture content

The terrestrial carbon cycle and the role of atmospheric CO₂ concentrations in controlling global temperatures can be inferred from the study of ancient soils (paleosols). Soil-formed goethite and calcite have been the primary minerals used as a geochemical proxy for reconstructing atmospheric pCO₂ from ancient terrestrial records. In the case of goethite, optimum sampling strategies for reconstructing pCO₂ focus on the portion of the soil profile that displays steep gradients in both soil CO₂ concentration and δ¹³C values of soil CO₂ such that a keeling plot can be developed for a given soil and atmospheric pCO₂ can be calculated from it. We report data from a Carboniferous paleosol that depart from the expected linear trends. The results indicate that pedogenic goethite is sensitive to variations in the isotopic composition of soil CO₂, over a range of timescales, and can record these variations in the carbon isotope composition and mole fraction of Fe(CO₃)OH in solid solution with goethite. We explore possible environmental conditions that can drive these changes as a function of either moisture controlled variations in soil respired CO₂ or in the residence time of carbon in soils. The implications of this result are overestimation of paleoatmospheric pCO₂ from pedogenic goethite.     

CO2流体对火山碎屑岩改造作用的实验研究

以塔木察格盆地火山碎屑岩为研究对象,研究不同温度下(100、120、140、160、180℃)CO2流体对火山碎屑岩(流纹质凝灰岩、沉凝灰岩)成分的改造.研究发现:在CO2流体的作用下,火山碎屑岩中的长石、碳酸盐矿物发生溶蚀,且其溶蚀强度随温度的升高而增大,石英的溶蚀程度较弱;火山碎屑岩中的凝灰质成分易溶蚀,并且是CO2流体溶蚀火山碎屑岩的主要对象;通过扫描电镜观察发现沉凝灰岩在160℃下样品表面有绿泥石(?)和一水软铝石(?)生成.结合塔木察格盆地中的碳酸盐矿物(尤其是片钠铝石)的存在及盆地中次生溶孔大量发育的特征,认为盆地内有CO2流体活动且CO2流体对塔木察格盆地次生孔隙的形成有重要的贡献.     

BRYOCARB: A process-based model of thallose liverwort carbon isotope fractionation in response to CO2, O2, light and temperature

Evidence from laboratory experiments indicates that fractionation against the heavy stable isotope of carbon (Δ¹³C) by bryophytes (liverworts and mosses) is strongly dependent on atmospheric CO₂. This physiological response may therefore provide the basis for developing a new terrestrial CO₂ proxy [Fletcher, B.J., Beerling, D.J., Brentnall, S.J., Royer, D.L., 2005. Fossil bryophytes as recorders of ancient CO₂ levels: experimental evidence and a Cretaceous case study. Global Biogeochem. Cycles19, GB3012]. Here, we establish a theoretical basis for the proxy by developing an extended model of bryophyte carbon isotope fractionation (BRYOCARB) that integrates the biochemical theory of photosynthetic CO₂ assimilation with controls on CO₂ supply by diffusion from the atmosphere. The BRYOCARB model is evaluated against measurements of the response of liverwort photosynthesis and Δ¹³C to variations in atmospheric O₂, temperature and irradiance at different CO₂ concentrations. We show that the bryophyte proxy is at least as sensitive to variations in atmosphere CO₂ as the two other leading carbon isotope-based approaches to estimating palaeo-CO₂ levels (δ¹³C of phytoplankton and of paleosols). Mathematical inversion of BRYOCARB provides a mechanistic means of estimating atmospheric CO₂ levels from fossil bryophyte carbon that can explicitly account for the effects of past differences in O₂ and climate.     

Mitigation of asphaltics deposition during CO2 flood by enhancing CO2 solvency with chemical modifiers

CO₂ injected in the reservoir of McElroy Field, TX, for a CO₂ flood was in the supercritical state. Supercritical CO₂ fluid is capable of extracting light and intermediate hydrocarbons from rocks but is unable to extract heavy hydrocarbons and asphaltics. Therefore, plugging of asphaltics in reservoir rocks and a consequent reduction in injectivity and recovery may result when CO₂ only is used in enhanced oil recovery. By adding common solvents as chemical modifiers, the flooding fluid shows marked improvement in solvency for heavy components of crudes due to its increased density and polarity. Numerous supercritical CO₂ fluid extractions of dolomite rock from the Grayburg Formation containing known amount of spiked McElroy crude oil have been carried out to evaluate extraction efficiencies of CO₂ and CO₂ with chemical modifiers at various temperatures and pressures. All experiments show that extraction efficiency increases with increasing CO₂ pressure but decreases with increasing temperature. Addition of chemical modifiers to CO₂ also shows improved extraction efficiency and reduced asphaltic deposits. Under the pressure and temperature similar to McElroy reservoir conditions; chemically modified CO₂ yielded almost 3 times as much oil extracts as those in extractions with CO₂ only. It also reduced the asphaltics content in extracted rocks to nearly one half; indicating its potential for mitigating asphaltics plugging of formation rocks     

Raman spectroscopic study of CO2-NaCl-H2O mixtures in synthetic fluid inclusions at high temperatures

Mixtures of CO₂-NaCl-H₂O contained in synthetic fluid inclusions are studied by laser Raman spectroscopy at high temperatures. With increasing temperature, the band splitting (X) of υ₁-2υ₂ diad of spectrum of CO₂ presents more variations, and the intensity ratios of the hot bands to the υ₁-2υ₂ diad increase. For mixtures of gas phase rich in CO₂ and liquid phase rich in H₂O before homogenization, the strength of hydrogen bonding of water in the liquid phase decreases almost linearly with increasing temperature. When mixtures become homogeneous liquid phases, carbon dioxide content increases significantly as a result of the abrupt decrease in hydrogen bonds. Our results show that the hydrogen bonds change only slightly at higher temperatures above the homogeneous point, and a certain extent of the hydrogen bonds still remains at the highest temperature of 550°C of this work. The study is helpful to Raman spectroscopic analysis of natural fluid inclusions at high temperatures.     

极富CO_2流体的造山型金矿:苏丹哈马迪金矿

哈马迪金矿位于苏丹东北部,矿床产于阿拉伯-努比亚地盾新元古界变质岩系中,属于受剪切带控制的造山型金矿床。金矿体赋存在角闪片岩内近南北向的片理化蚀变带中,围岩蚀变主要为黄铁绢英岩化,以及绿泥石化和碳酸盐化等。在含矿石英细脉中赋存有大量的极富CO2的碳质流体包裹体。这些包裹体几乎不含水,含有少量CH4(XCH4=0~0.10)。脉石英中碳质流体包裹体既有孤立或随机分布的原生包裹体,也有呈线性分布的次生包裹体,最晚期还有次生水溶液包裹体的分布。碳质流体包裹体的三相点(Tm,CO2)范围变化不大(-58.4~-57.0℃),但均一温度(Th,CO2)范围变化较大(-19℃~+29℃)。捕获的P-T条件可由LCO2包裹体的ρ值或Th,CO2值,以及与其伴生的CO2-H2O包裹体最终均一温度Th,TOT值,从有关相图中估算。早期碳质流体包裹体的捕获P-T条件范围为280~360℃、80~320MPa。金矿化发生在变质峰期之后的退变质作用晚期。广泛发育的热液蚀变说明碳质流体并非来自单一的流体源,寄主石英变形很弱也不能解释水从H2O-CO2-盐流体包裹体中优先淋失、残留大量的CO2±CH4包裹体。碳质流体包裹体可能的成因是:在金成矿的退变质时期,来自深部的H2O-CO2-盐流体,由于P-T下降而发生不混溶,H2O在热液蚀变中被大量消耗,而CO2则以碳质流体包裹体的形式被得捕获在脉石英中。     

CO2-H2O mixtures in the geological sequestration of CO2. I. Assessment and calculation of mutual solubilities from 12 to 100°C and up to 600 bar

Evaluating the feasibility of CO₂ geologic sequestration requires the use of pressure-temperature-composition (P-T-X) data for mixtures of CO₂ and H₂O at moderate pressures and temperatures (typically below 500 bar and below 100°C). For this purpose, published experimental P-T-X data in this temperature and pressure range are reviewed. These data cover the two-phase region where a CO₂-rich phase (generally gas) and an H₂O-rich liquid coexist and are reported as the mutual solubilities of H₂O and CO₂ in the two coexisting phases. For the most part, mutual solubilities reported from various sources are in good agreement. In this paper, a noniterative procedure is presented to calculate the composition of the compressed CO₂ and liquid H₂O phases at equilibrium, based on equating chemical potentials and using the Redlich-Kwong equation of state to express departure from ideal behavior. The procedure is an extension of that used by King et al. (1992), covering a broader range of temperatures and experimental data than those authors, and is readily expandable to a nonideal liquid phase. The calculation method and formulation are kept as simple as possible to avoid degrading the performance of numerical models of water-CO₂ flows for which they are intended. The method is implemented in a computer routine, and inverse modeling is used to determine, simultaneously, (1) new Redlich-Kwong parameters for the CO₂-H₂O mixture, and (2) aqueous solubility constants for gaseous and liquid CO₂ as a function of temperature. In doing so, mutual solubilities of H₂O from 15 to 100°C and CO₂ from 12 to 110°C and up to 600 bar are generally reproduced within a few percent of experimental values. Fugacity coefficients of pure CO₂ are reproduced mostly within one percent of published reference data.