Combined microthermometric and Raman spectroscopic technique to determine the salinity of H2O-CO2-NaCl fluid inclusions based on clathrate melting

Fluid inclusions approximated by the system H₂O-CO₂-NaCl are common in many geologic environments. In order to apply microthermometric data from these inclusions to infer P-T (pressure-temperature) trapping conditions, the composition of the inclusions, including the salinity, must be known. Normally, salinities of aqueous inclusions are determined from ice-melting temperatures obtained during microthermometry. However, when CO₂-bearing aqueous fluid inclusions are cooled they often form a hydrate that incorporates H₂O into the structure, and salinities estimated from ice-melting temperatures are therefore higher than the actual salinity. A technique that combines data from Raman spectroscopic and microthermometric analyses of individual inclusions was developed to determine the salinity of CO₂-bearing aqueous inclusions based on measured clathrate melting temperatures and CO₂ pressures obtained from Raman analyses. In this study, the pressure within inclusions was determined using Raman spectroscopy based on the splitting of the Fermi diad of CO₂, measured at the clathrate melting temperature. The CO₂ densities (and pressures) predicted by the equation developed in this study are in relatively good agreement with previously published equations, except for very low densities and correspondingly low pressures. The combined Raman spectroscopy - microthermometry technique thus provides both the temperature and the pressure in the inclusion at clathrate melting. For inclusions in which the clathrate melts in the presence of CO₂ liquid, the salinity can be determined with a precision of a few tenths of a wt% NaCl, whereas for inclusions in which clathrate melts in the presence of CO₂ vapor the salinity error may be a few wt% NaCl. Applying the method to synthetic fluid inclusions with known salinity suggests that the technique is valid for determining salinity of H₂O-CO₂-NaCl fluid inclusions in which clathrate melts in the presence of liquid CO₂ only or vapor CO₂ only.     

A unified equation for calculating methane vapor pressures in the CH4-H2O system with measured Raman shifts

A unified equation has been derived by using all available data for calculating methane vapor pressures with measured Raman shifts of C-H symmetric stretching band (υ₁) in the vapor phase of sample fluids near room temperature. This equation eliminates discrepancies among the existing data sets and can be applied at any Raman laboratory. Raman shifts of C-H symmetric stretching band of methane in the vapor phase of CH₄-H₂O mixtures prepared in a high-pressure optical cell were also measured at temperatures between room temperature and 200 °C, and pressures up to 37 MPa. The results show that the CH₄υ₁ band position shifts to higher wavenumber as temperature increases. We also demonstrated that this Raman band shift is a simple function of methane vapor density, and, therefore, when combined with equation of state of methane, methane vapor pressures in the sample fluids at elevated temperatures can be calculated from measured Raman peak positions. This method can be applied to determine the pressure of CH₄-bearing systems, such as methane-rich fluid inclusions from sedimentary basins or experimental fluids in hydrothermal diamond-anvil cell or other types of optical cell.     

Raman spectroscopic measurements of CO2 density: Experimental calibration with high-pressure optical cell (HPOC) and fused silica capillary capsule (FSCC) with application to fluid inclusion observations

Raman spectroscopy is a powerful method for the determination of CO₂ densities in fluid inclusions, especially for those with small size and/or low fluid density. The relationship between CO₂ Fermi diad split (Δ, cm⁻¹) and CO₂ density (ρ, g/cm³) has been documented by several previous studies. However, significant discrepancies exist among these studies mainly because of inconsistent calibration procedures and lack of measurements for CO₂ fluids having densities between 0.21 and 0.75 g/cm³, where liquid and vapor phases coexist near room temperature.In this study, a high-pressure optical cell and fused silica capillary capsules were used to prepare pure CO₂ samples with densities between 0.0472 and 1.0060 g/cm³. The measured CO₂ Fermi diad splits were calibrated with two well established Raman bands of benzonitrile at 1192.6 and 1598.9 cm⁻¹. The relationship between the CO₂ Fermi diad split and density can be represented by: ρ = 47513.64243 − 1374.824414 × Δ + 13.25586152 × Δ² − 0.04258891551 × Δ³ (r² = 0.99835, σ = 0.0253 g/cm³), and this relationship was tested by synthetic fluid inclusions and natural CO₂-rich fluid inclusions. The effects of temperature and the presence of H₂O and CH₄ on this relationship were also examined.     

Thermodynamic modeling of binary CH4-H2O fluid inclusions

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/.     

A Study of Ore-forming Fluids in the Shimensi Tungsten Deposit, Dahutang Tungsten Polymetallic Ore Field, Jiangxi Province, China

The Dahutang tungsten polymetallic ore field is located north of the Nanling W-Sn polymetallic metallogenic belt and south of the Middle—Lower Yangtze River Valley Cu-Mo-Au-Fe porphyry-skarn belt.It is a newly discovered ore field,and probably represents the largest tungsten mineralization district in the world.The Shimensi deposit is one of the mineral deposits in the Dahutang ore field,and is associated with Yanshanian granites intruding into a Neoproterozoic granodiorite batholith.On the basis of geologic studies,this paper presents new petrographic,microthermometric,laser Raman spectroscopic and hydrogen and oxygen isotopic studies of fluid inclusions from the Shimensi deposit.The results show that there are three types of fluid inclusions in quartz from various mineralization stages:liquid-rich two-phase fluid inclusions,vapor-rich two-phase fluid inclusions,and three-phase fluid inclusions containing a solid crystal,with the vast majority being liquid-rich two-phase fluid inclusions.In addition,melt and melt-fluid inclusions were also found in quartz from pegmatoid bodies in the margin of the Yanshanian intrusion.The homogenization temperatures of liquid-rich two-phase fluid inclusions in quartz range from 162 to 363℃ and salinities are 0.5wt%-9.5wt%NaCI equivalent.From the early to late mineralization stages,with the decreasing of the homogenization temperature,the salinity also shows a decreasing trend.The ore-forming fluids can be approximated by a NaCl-H_2O fluid system,with small amounts of volatile components including CO_2,CH_4 and N_2,as suggested by Laser Raman spectroscopic analyses.The hydrogen and oxygen isotope data show that δ5D_(V-smow) values of bulk fluid inclusions in quartz from various mineralization stages vary from-63.8‰ to-108.4‰,and the δ~(18)O_(H2O) values calculated from the δ~(18)O_(V-)smow values of quartz vary from-2.28‰ to 7.21‰.These H-O isotopic data are interpreted to indicate that the ore-forming fluids are mainly composed of magmatic water in the early stage,and meteoric water was added and participated in mineralization in the late stage.Integrating the geological characteristics and analytical data,we propose that the ore-forming fluids of the Shimensi deposit were mainly derived from Yanshanian granitic magma,the evolution of which resulted in highly differentiated melt,as recorded by melt and melt-fluid inclusions in pegmatoid quartz,and high concentrations of metals in the fluids.Cooling of the ore-forming fluids and mixing with meteoric water may be the key factors that led to mineralization in the Dahutang tungsten polymetallic ore field.     

Juvenile CO2 in enderbites of Tromøy near Arendal, southern Norway: a fluid inclusion and stable isotope study

The enderbites from Tromøy in the central, granulite facies part of the Proterozoic Bamble sector of southern Norway contain dominantly CO₂ and N₂ fluid inclusions. CO₂ from fluid inclusions in quartz segregations in enderbites was extracted by mechanical (crushing) and thermal decrepitation and the δ¹³C measured. Measurement was also made on samples washed in 10% HCl, oxidized with CuO at high temperatures, and step-wise extracted with progressive heating. Results between the different techniques are systematic. The main results show δ¹³C of -4.5±1.5% for crushing and -7±2% for thermal decrepitation. δ¹³C is about constant for CO₂ extracted at different temperatures and points to a homogeneous isotopic composition. Due to the presence of carbonate particles and/or induced contaminations for the extraction by thermal decrepitation, the results for the crushing experiments are assumed the most reliable for fluid-inclusion CO₂. Very low values of δ¹³C have not been found in enderbite samples and δ¹³C combined with δ¹⁸O of the host quartzes (8-11%) indicates juvenile values. In addition, the fluid inclusions were examined by microthermometry and Raman analysis and host quartz by acoustic emission and cathodoluminescence. CO₂ fluid inclusions have varying densities with a frequency maximum of 0.92 g cm^-3 and generally do not concur with trapping densities at granulite conditions. Textures show that CO₂ must have been trapped in fluid inclusions in one early event, but transformed to different extents during late isothermal uplift without important fractionation of isotope compositions. The present data support a model of intrusion and crystallization of a CO₂-rich enderbitic magma at granuiite conditions.     

Synthetic fluid inclusions in natural quartz. III. Determination of phase equilibrium properties in the system H2O-NaCl to 1000°C and 1500 bars

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.     

Etude des inclusions fluides du système N2-CO2 de dolomites et de quartz de Tunisie septentrionale. Données de la microcryoscopie et de l'analyse à la microsonde à effet Raman

Optical and analytical studies were performed on 400 N₂ + CO₂ gas bearing inclusions in dolomites and quartz from Triassic outcrops in northern Tunisia. Other fluids present include brines (NaCl and KCl bearing inclusions) and rare liquid hydrocarbons. At the time of trapping, such fluids were heterogeneous gas + brine mixtures. In hydrocarbon free inclusions the $\text{N}{}_2\text{(N}{}_2\text{+ CO}{}_2\text{)}$ mole ratio was determined using two different non-destructive and punctual techniques: Raman microprobe analysis, and optical estimation of the volume ratios of the different phases selected at low temperatures. In the observed range of compositions, the two methods agree reasonably well.The N₂ + CO₂ inclusions are divided into three classes of composition: (a) $\text{N}{}_2\text{(N}{}_2\text{+ CO}{}_2\text{)}\text{> 0,57}$: Liquid nitrogen is always visible at very low temperature and homogenisation occurs in the range ?151°C to ? 147°C (nitrogen critical temperature) dry ice (solid CO₂) sublimates between ?75°C and ?60°C; (b) $\text{0,20 <}\text{N}{}_2\text{(N}{}_2\text{+ CO}{}_2\text{)}\text{? 0,57}$: liquid nitrogen is visible at very low temperature but dry ice melts on heating; liquid and gas CO₂ homogenise to liquid phase between ?51°C to ?22°C; (c) $\text{N}{}_2\text{(N}{}_2\text{+ CO}{}_2\text{)}\text{? 0,20}$: liquid nitrogen is not visible even at very low temperature (?195°C) and liquid and gas CO₂ homogenise to liquid phase between ?22°C and ?15°C. The observed phases changes are used to propose a preliminary phase diagram for the system CO₂-N₂ at low temperatures.Assuming additivity of partial pressures, isochores for the CO₂-N₂ inclusions have been computed. The intersection of these isochores with those for brine inclusions in the same samples may give the P and T of trapping of the fluids.     

Re-equilibration of CO2 fluid inclusions at controlled hydrogen fugacities

Abstract Natural, pure CO₂ inclusions in quartz and olivine (c. Fo₉₀) were exposed to controlled f_H2 conditions at T= 718–728°C and P_total= 2 kbar; their compositions were monitored (before and after exposures) by microsampling Raman spectroscopy (MRS) and microthermometry. In both minerals exposed at the graphite–methane buffer (f_H2= 73 bar), fluid speciations record the diffusion of hydrogen into the inclusions. In quartz, room-temperature products in euhedral isolated (EI type) inclusions are carbonic phases with molar compositions of c. CO₂(60) + CH₄(40) plus graphite (Gr) and H₂O, whereas anhedral inclusions along secondary fractures (AS type) are Gr-free and contain H₂O plus carbonic phases with compositions in the range c. CO₂(60) + CH₄(40) to CO₂(10) + CH₄(90). EI type inclusions in olivine evolved to c. CO₂(90–95) + CH₄(5–10) without Gr, whereas AS type inclusions have a range of compositions from CO₂(90) + CH₄(10) ± Gr to CH₄(50) + H₂(50) ± Gr; neither H₂O nor any hydrous species was detected by optical microscopy or MRS in the olivine-hosted products. Differences in composition between and among the texturally distinct populations of inclusions in both minerals probably arise from variations in initial fluid densities, as all inclusions apparently equilibrated with the ambient f_H2. These relations suggest that compositional variability among inclusions in a given natural sample does not require the entrapment of multiple generations of fluids. In addition, the absence of H₂O in the olivine-hosted inclusions would require the extraction of oxygen from the fluids, in which case re-equilibration mechanisms may be dependent on the composition and structure of the host mineral. Many of the same samples were re-exposed to identical P–T conditions using Ar as the pressure medium, yielding ambient f_H2= 0.06 bar. In most inclusions, the carbonic fluids returned to pure CO₂ and graphite persisted in the products. Reversal of the mechanisms from the prior exposure at f_H2= 73 bar did not occur in any inclusions but the AS types in olivine, in which minor CO₂ was produced at the expense of CH₄ and/or graphite. The observed non-reversibility of previous mechanisms may be attributed to: (1) slower fluid–solid reactions compared to reactions in the homogeneous fluid phase; (2) depressed activities of graphite due to poor ordering; and/or (3) low ambient f_O2 at the conditions of the second run.     

Phase equilibria in fluid inclusions from the Khtada Lake metamorphic complex

The Khtada Lake. British Columbia, metamorphic complex consists of high grade amphibolite and metasedimentary units with development of gneiss, migmatite and homogeneous autochthonous plutons. Maximum metamorphic conditions are estimated to have exceeded 5 kbar and 700°C.Fluid inclusions in matrix quartz are highly variable in density and composition, ranging from apparently pure CO₂ (gas or liquid or both at room temperature) through CO₂ + H₂O ± CH₄ mixtures to inclusions which are entirely aqueous. They occur along cracks, in groups without planar features and as isolated inclusions. The latter and some which occur in groups, are interpreted to most nearly approximate, in density and composition, the fluids present during the peak of metamorphism.The density and fluid composition data are derived from direct observations of phase changes between ? 180 and + 380°C and from the application of published experimental data in the system CH₄-CO₂-H₂O-NaCl. The most dense, pure CO₂ inclusions indicate a pressure of entrapment at 5 kbar, if a temperature of 700°C is assumed. This is in close agreement with the minimum P-T estimates from the mineral assemblages. Methane was positively identified in inclusions in graphite-bearing specimens. Salt content is concluded to be about 5–6 wt% NaCl equivalent in the aqueous phase in both aqueous and CO₂ + H₂O inclusions. There is evidence of immiscible separation of CO₂-rich and H₂O-rich fluids at temperatures at least as high as 375°C.     

赤城县梁家沟铅锌银多金属矿床流体包裹体特征及其意义

文章运用激光拉曼光谱和显微测温等方法,对赤城县梁家沟铅锌银多金属矿床矿石中的石英流体包裹体进行均一温度、盐度的测试分析。结果表明,矿物中的流体包裹体以气液2相为主,气相成分主要是CO2,液相成分主要是H2O和烃类液体;包裹体的均一温度为80.0~160.0℃,盐度w(NaCl)=2%~12%,说明矿床形成条件为低温低盐度,且富含烃类物质。结合矿床地质特征、矿床的构造位置、产出地层和该矿床中矿(岩)石的常量元素、微量元素和稀土元素的数据研究结果,初步厘定梁家沟铅锌银矿床属于密西西比河谷型(MVT)矿床。     

Fluid Inclusions and C?H?O?S?Pb Isotopes: Implications for the Genesis of the Zhuanshanzi Gold Deposit on the Northern Margin of the North China Craton

The Zhuanshanzi gold deposit lies in the eastern section of the Xingmeng orogenic belt and the northern section of the Chifeng‐Chaoyang gold belt. The gold veins are strictly controlled by a NW‐oriented shear fault zone. Quartz veins and altered tectonic rock‐type gold veins are the main vein types. The deposits can be divided into four mineralization stages, and the second and third metallogenic stages are the main metallogenic stages. In this paper, based on the detailed field geological surveys, an analysis of the orebody and ore characteristics, microtemperature measurement of fluid inclusions, the Laser Raman spectrum of the inclusions, determination of C? H? O? S? Pb isotopic geochemical characteristics, and so on were carried out to explore the origin of the ore‐forming fluids, ore‐forming materials, and the genesis of the deposits. The results show that the fluid inclusions can be divided into four types: type I – gas–liquid two‐phase inclusions; type II – gas‐rich inclusions; type III– liquid inclusions; and type IV – CO₂‐containing three‐phase inclusions. However, they are dominated by type Ib – gas liquid inclusions and type IV – three‐phase inclusions containing CO₂. The gas compositions are mainly H₂O and CO₂, indicating that the metallogenic system is a CO₂? H₂O? NaCl system. The homogenization temperature of the ore‐forming fluid evolved from a middle temperature to a low temperature, and the temperature of the fluid was further reduced due to meteoric water mixing during the late stage, as well as a lack of CO₂ components, and eventually evolved into a simple NaCl? H₂O hydrothermal system. C? H? O? S? Pb isotope research proved that the ore‐forming fluids are mainly magmatic water during the early stage, with abundant meteoric water mixed in during the late stage. Ore‐forming materials originated mostly from hypomagma and were possibly influenced by the surrounding rocks, suggesting that the ore‐forming materials were mainly magmatic hydrothermal deposits, with a small amount of crustal component. The fluid immiscibility and the CO₂ and CH₄ gases in the fluids played an active and important role in the precipitation and enrichment of Au during different metallogenic stages. The deposit is considered a magmatic hydrothermal deposit of middle–low temperature.     

Reactive flow of mixed CO2–H2O fluid and progress of calc-silicate reactions in contact metamorphic aureoles: insights from two-dimensional numerical modelling

Previous models of hydrodynamics in contact metamorphic aureoles assumed flow of aqueous fluids, whereas CO₂ and other species are also common fluid components in contact metamorphic aureoles. We investigated flow of mixed CO₂–H₂O fluid and kinetically controlled progress of calc‐silicate reactions using a two‐dimensional, finite‐element model constrained by the geological relations in the Notch Peak aureole, Utah. Results show that CO₂ strongly affects fluid‐flow patterns in contact aureoles. Infiltration of magmatic water into a homogeneous aureole containing CO₂–H₂O sedimentary fluid facilitates upward, thermally driven flow in the inner aureole and causes downward flow of the relatively dense CO₂‐poor fluid in the outer aureole. Metamorphic CO₂‐rich fluid tends to promote upward flow in the inner aureole and the progress of devolatilization reactions causes local fluid expulsion at reacting fronts. We also tracked the temporal evolution of P‐T‐X_CO2conditions of calc‐silicate reactions. The progress of low‐ to medium‐grade (phlogopite‐ to diopside‐forming) reactions is mainly driven by heat as the CO₂ concentration and fluid pressure and temperature increase simultaneously. In contrast, the progress of the high‐grade wollastonite‐forming reaction is mainly driven by infiltration of chemically out‐of‐equilibrium, CO₂‐poor fluid during late‐stage heating and early cooling of the inner aureole and thus it is significantly enhanced when magmatic water is involved. CO₂‐rich fluid dominates in the inner aureole during early heating, whereas CO₂‐poor fluid prevails at or after peak temperature is reached. Low‐grade metamorphic rocks are predicted to record the presence of CO₂‐rich fluid, and high‐grade rocks reflect the presence of CO₂‐poor fluid, consistent with geological observations in many calc‐silicate aureoles. The distribution of mineral assemblages predicted by our model matches those observed in the Notch Peak aureole.     

Depth of volcanic basalt degassing forecasted from CO2 fluid inclusions

Fluid inclusions have recorded the history of degassing in basalt. Some fluid inclusions in olivine and pyroxene phenocrysts of basalt were analyzed by micro-thermometry and Raman spectroscopy in this paper. The experimental results showed that many inclusions are present almost in a pure CO2 system. The densities of some CO2 inclusions were computed in terms of Raman spectroscopic characteristics of CO2 Fermi resonance at room temperature. Their densities change over a wide range, but mainly between 0.044 g/cm3 and 0.289 g/cm3. Their micro-thermometric measurements showed that the CO2 inclusions examined reached homogenization between 1145.5℃ and 1265℃ . The mean value of homogenization temperatures of CO2 inclusions in basalts is near 1210℃. The trap pressures (depths) of inclusions were computed with the equation of state and computer program. Distribution of the trap depths makes it know that the degassing of magma can happen over a wide pressure (depth) range, but mainly at the depth of 0.48 km to 3.85 km. This implicates that basalt magma experienced intensive degassing and the CO2 gas reservoir from the basalt magma also may be formed in this range of depths. The results of this study showed that the depth of basalt magma degassing can be forecasted from CO2 fluid inclusions, and it is meaningful for understanding the process of magma degassing and constraining the inorganogenic CO2 gas reservoir.     

CO<Subscript>2</Subscript> fluid inclusions in Jack Hills zircons

The discovery of Hadean to Paleoarchean zircons in a metaconglomerate from Jack Hills, Western Australia, has catalyzed intensive study of these zircons and their mineral inclusions, as they represent unique geochemical archives that can be used to unravel the geological evolution of early Earth. Here, we report the occurrence and physical properties of previously undetected CO₂ inclusions that were identified in 3.36–3.47 Ga and 3.80–4.13 Ga zircon grains by confocal micro-Raman spectroscopy. Minimum P–T conditions of zircon formation were determined from the highest density of the inclusions, determined from the density-dependence of the Fermi diad splitting in the Raman spectrum and Ti-in-zircon thermometry. For both age periods, the CO₂ densities and Ti-in-zircon temperatures correspond to high-grade metamorphic conditions (≥5 to ≥7 kbar/~670 to 770 °C) that are typical of mid-crustal regional metamorphism throughout Earth’s history. In addition, fully enclosed, highly disordered graphitic carbon inclusions were identified in two zircon grains from the older population that also contained CO₂ inclusions. Transmission electron microscopy on one of these inclusions revealed that carbon forms a thin amorphous film on the inclusion wall, whereas the rest of the volume was probably occupied by CO₂ prior to analysis. This indicates a close relationship between CO₂ and the reduced carbon inclusions and, in particular that the carbon precipitated from a CO₂-rich fluid, which is inconsistent with the recently proposed biogenic origin of carbon inclusions found in Hadean zircons from Jack Hills.     

An experimental study of phase equilibria in the systems H2O–CO2–CaCl2 and H2O–CO2–NaCl at high pressures and temperatures (500–800?°C, 0.5–0.9?GPa): geological and geophysical applications

Phase equilibria in the ternary systems H₂O–CO₂–NaCl and H₂O–CO₂–CaCl₂ have been determined from the study of synthetic fluid inclusions in quartz at 500 and 800 °C, 0.5 and 0.9 GPa. The crystallographic control on rates of quartz overgrowth on synthetic quartz crystals was exploited to prevent trapping of fluid inclusions prior to attainment of run conditions. Two types of fluid inclusion were found with different density or CO₂ homogenisation temperature (T_h(CO₂)): a CO₂-rich phase with low T_h(CO₂), and a brine with relatively high T_h(CO₂). The density of CO₂ was calibrated using inclusions in the binary system H₂O–CO₂. Mass balance calculations constrain tie lines and the miscibility gap between brines and CO₂-rich fluids in the H₂O–CO₂–NaCl and H₂O–CO₂–CaCl₂ systems at 500 and 800 °C, and 0.5 and 0.9 GPa. The miscibility gap in the CaCl₂ system is larger than in the NaCl system, and solubilities of CO₂ are smaller. CaCl₂ demonstrates a larger salting-out effect than NaCl at the same P–T conditions. In ternary systems, homogeneous fluids are H₂O-rich and of extremely low salinity, but at medium to high concentrations of salts and non-polar gases fluids are unlikely to be homogeneous. The two-phase state of crustal fluids should be common. For low fluid-rock ratios the cation compositions of crustal fluids are buffered by major crustal minerals: feldspars and micas in pelites and granitic rocks, calcite (dolomite) in carbonates, and pyroxenes and amphiboles in metabasites. Fluids in pelitic and granitic rocks are Na-K rich, while for carbonate and metabasic rocks fluids are Ca-Mg-Fe rich. On lithological boundaries between silicate and carbonate rocks, or between pelites and metabasites, diffusive cation exchange of the salt components of the fluid will cause the surfaces of immiscibility to intersect, leading to unmixing in the fluid phase. Dispersion of acoustic energy at critical conditions of the fluid may amplify seismic reflections that result from different fluid densities on lithological boundaries.Editorial responsibility: I. Parsons     

长岭凹陷深层天然气藏中CO_2及CH_4充注次序的流体包裹体证据

对长岭凹陷深层天然气藏储层——营城组火山岩中发育的流体包裹体进行了详细研究,结果表明在火山岩发育的石英、方解石细网脉中均存在较多的碳质流体包裹体,单个包裹体激光拉曼光谱分析结果表明其主要为CO2及CH4两种类型的碳质包裹体。其中方解石细网脉体中发育有原生及次生CH4包裹体,而含CO2包裹体多以原生包裹体产于石英细网脉中。很多含CO2包裹体的石英细脉中发现了含CH4包裹体的方解石脉体的角砾,这就表明石英细脉形成晚于方解石细脉。营城组火山岩储层中CO2及CH4包裹体的产状特征研究表明,松辽盆地深层天然气藏的形成系火山岩成岩后CO2及CH4等气体不同期次充注的结果,CH4气的充注时间早于CO2气,火山岩中发育的原生孔隙及次生裂隙为上述气体的充注和聚集提供了重要通道。     

An empirical solvus for CO2-H2O-2.6 wt% salt

The solvus in the system CO₂-H₂O-2.6 wt% NaCl-equivalent was determined by measuring temperature of homogenization in fluid inclusions which contained variable $\text{CO}{}_2\text{H}{}_2\text{O}$ but the same amount of salt dissolved in the aqueous phase at room temperature. The critical point of the solvus is at 340 ± 5°C, at pressures between 1 and 2 kbar; this is about 65°C higher than for the pure CO₂-H₂O system. The solvus is assymetrical, with a steeper H₂O-rich limb and with the critical point at mole fraction of water between 0.65 and 0.8.     

Role of fluids in migmatites: CO2-H2O fluid inclusions in leucosomes from the Deep Freeze Range migmatites (Terra Nova Bay, Antarctica)

ABSTRACT The metasedimentary sequence of the Deep Freeze Range (northern Victoria Land, Antarctica) experienced high-T/low-F metamorphism during the Cambro-Ordovician Ross orogeny. The reaction Bt + Sil + Qtz = Grt + Crd + Kfs + melt was responsible for the formation of migmatites. Peak conditions were c. 700–750° C, c. 3.5–5 kbar and x_H2Oc. 0.5). Distribution of fluid inclusions is controlled by host rock type: (1) CO₂-H₂O fluid inclusions occur only in graphite-free leucosomes; (2) CO₂–CH₄± H₂O fluid inclusions are the most common type in leucosomes, and in graphite-bearing mesosomes and gneiss; and (3) CO₂–N₂–CH₄ fluid inclusions are observed only in the gneiss, and subordinately in mesosomes. CO₂–H₂O mixtures (41% CO₂, 58% H₂O, 1% Nad mol.%) are interpreted as remnants of a synmig-matization fluid; their composition and density are compatible P–T–a_H2O conditions of migmatization (c. 750° C, c. 4 kbar, x_H2Oc. 0.5). CO₂-H₂O fluid in graphite-free leucosomes cannot originate via partial melting of graphite-bearing mesosomes in a closed system; this would have produced a mixed CO₂–CH₄ fluid in the leucosomes by a reaction such as Bt + Sil + Qtz + C ± H₂O = Grt + Crd + Kfs + L + CO₂+ CH₄. We conclude that an externally derived oxidizing CO₂-H₂O fluid was present in the middle crust and initiated anatexis. High-density CO₂-rich fluid with traces of CH₄ characterizes the retrograde evolution of these rocks at high temperatures and support isobaric cooling (P–T anticlockwise path). In unmigmatized gneiss, mixed CO₂–N₂–CH₄ fluid yields isochores compatible with peak metamorphic conditions (c. 700–750° C, c. 4–4.5 kbar); they may represent a peak metamorphic fluid that pre-dated the migmatization.