We first report discovery of the spinel-garnet-orthopyroxene granulite with pure CO2 fluid inclusions from the Fuyun region of the late Paleozoic Altay orogenic belt in Central Asia, NW China. The rock is characterize...We first report discovery of the spinel-garnet-orthopyroxene granulite with pure CO2 fluid inclusions from the Fuyun region of the late Paleozoic Altay orogenic belt in Central Asia, NW China. The rock is characterized by an assemblage of garnet, orthopyroxene, spinel, cordierite, biotite, plagioclase and quartz. Symplectites of orthopyroxene and spinel, and orthopyroxene and cordierite indicate decompression under UHT conditions. Mineral chemistry shows that the or-thopyroxenes have high XMg and A12O3 contents (up to 9.23 wt%). Biotites are enriched in TiO2 and XMg and are stable under granulite facies conditions. The garnet and quartz from the rock carry monophase fluid inclusions which show peak melting temperatures of around -56.7℃, indicating a pure CO2 species being presented during the ultrahigh-T metamorphism in the Altay orogenic belt. The inclusions homogenize into a liquid phase at temperatures around 15.3-23.8℃ translating into CO2 densities of the order of 0.86-0.88 g/cm3. Based on preliminary mineral paragenesis, reaction textures and petrogenetic grid considerations, we infer that the rock was subjected to UHT conditions. The CO2-rich fluids were trapped during exhumation along a clockwise P-T path following isothermal decompression under UHT conditions.展开更多
We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,ind...We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,indicating that Raman quantification of CH4/CO2 molar ratio can be applied to those fluid inclusions(FIs)with high internal pressure(i.e.,>15 MPa).Secondly,the v1(CH4)peak position shifts to lower wavenumber with increasing pressure at constant temperature,confirming that the v1(CH4)peak position can be used to calculate the fluid pressure.However,this method should be carefully calibrated before applying to FI analyses because large discrepancies exist among the reported v1(CH4)-P curves,especially in the highpressure range.These calibrations are applied to CH4-rich FIs in quartz veins of the Silurian Longmaxi black shales in southern Sichuan Basin.The vapor phases of these FIs are mainly composed of CH4 and minor CO2,with CO2 molar fractions from4.4%to 7.4%.The pressure of single-phase gas FI ranges from 103.65 to 128.35 MPa at room temperature,which is higher than previously reported.Thermodynamic calculations supported the presence of extremely high-pressure CH4-saturated fluid(218.03–256.82 MPa at 200°C),which may be responsible for the expulsion of CH4 to adjacent reservoirs.展开更多
Previous cryogenic Raman spectroscopic analysis of H_2O-NaCl-CaCl_2 solutions has identified the Raman peaks of various hydrates of NaCl and CaCl_2,and established a linear relationship between Raman band intensity of...Previous cryogenic Raman spectroscopic analysis of H_2O-NaCl-CaCl_2 solutions has identified the Raman peaks of various hydrates of NaCl and CaCl_2,and established a linear relationship between Raman band intensity of the hydrates and the composition of the solution（NaCl/（NaCl＋CaCl_2） molar ratio,or X_（NaC1）） using synthetic fluids,which created the opportunity to quantitatively determine the solute composition of aqueous fluid inclusions with cryogenic Raman spectroscopy.This paper aims to test the feasibility of this newly established method with natural fluid inclusions.Twenty-five fluid inclusions in quartz from various occurrences which show a high degree of freezing during the cooling processes were carefully chosen for cryogenic Raman analysis.X_（Na）Cl was calculated using their spectra and an equation established in a previous study.These inclusions were then analyzed with the thermal decrepitation-SEM-EDS method.The X_（NaCl） values estimated from the two methods show a 1：1 correlation,indicating that the new,non-destructive cryogenic Raman spectroscopic analysis method can indeed be used for fluid inclusion compositional study.展开更多
The density of CO<sub>2</sub> inclusions in minerals is commonly used to determine the crystallizing conditions of the host minerals.However,the conventional microthermometry method is difficult to apply f...The density of CO<sub>2</sub> inclusions in minerals is commonly used to determine the crystallizing conditions of the host minerals.However,the conventional microthermometry method is difficult to apply for inclusions that are small in size（【5-10μm） or low in density.Raman analysis is an alternative method for determining CO<sub>2</sub> density,provided that展开更多
Methane-rich fluids were recognized to be hosted in the reservoir volcanic rocks as primary inclusions. Samples were collected from core-drillings of volcanic gas reservoirs with reversed δ13C of alkane in the Xujiaw...Methane-rich fluids were recognized to be hosted in the reservoir volcanic rocks as primary inclusions. Samples were collected from core-drillings of volcanic gas reservoirs with reversed δ13C of alkane in the Xujiaweizi depression of the Songliao Basin. The volcanic rocks are rhyolite dominant being enriched in the more incompatible elements like Cs, Rb, Ba, Th, U and Th with relative high LREE, depleted HREE and negative anomalies of Ti and Nb, suggesting a melt involving both in mantle source and crustal assimilation. Primary fluids hosted in the volcanic rocks should have the same provenance with the magma. The authors concluded that the enclosed CH4 in the volcanics are mantle/magma-derived alkane and the reversed δ13C of alkane in the corresponding gas reservoirs is partly resulted from mixture between biogenic and abiogenic gases.展开更多
Comparing compositions of the fluid inclusions in volcanic rocks to the contents and isotopes of the gases in corresponding volcanic reservoirs using microthermometry, Raman microspectroscopy and mass spectrum analysi...Comparing compositions of the fluid inclusions in volcanic rocks to the contents and isotopes of the gases in corresponding volcanic reservoirs using microthermometry, Raman microspectroscopy and mass spectrum analysis, we found that： （1） up to 82 mole% methane exists in the primary inclusions hosted in the reservoir volcanic rocks; （2） high CH4 inclusions recognized in the volcanic rocks correspond to CH4-bcaring CO2 reservoirs that are rich in helium and with a high ^3He/^4He ratio and which show reversed order of 813C in alkane; （3） in gas reservoirs of such abiotic methane （〉80%） and a mix of CH4 and CO2, the enclosed content of CH4 in the volcanic inclusions is usually below 42 mole%, and the reversed order of δ^13C in alkane is sometimes irregular in the corresponding gas pools; （4） a glassy inclusion with a homogeneous temperature over 900℃ also contains a small portion of CH4 although predominantly CO2. This affinity between gas pool and content of inclusion in the same volcanic reservoirs demonstrates that magma-originated gases, both CH4 and CO2, have contributed significantly to the corresponding gas pools and that the assumed hydrocarbon budget of the bulk earth might be much larger than conventionally supposed.展开更多
Reaction textures and fluid inclusions in the -2.0 Ga pyroxene-bearing dehydration zones within the Sand River biotite-hornblende orthogneisses （Central Zone of the Limpopo Complex） suggest that the formation of the...Reaction textures and fluid inclusions in the -2.0 Ga pyroxene-bearing dehydration zones within the Sand River biotite-hornblende orthogneisses （Central Zone of the Limpopo Complex） suggest that the formation of these zones is a result of close interplay between dehydration process along ductile shear zones triggered by H2O-CO2-salt fluids at 750--800 ℃ and 5.5--6.2 kbar, partial melting, and later exsolution of residual brine and H2O-CO2 fluids during melt crystallization at 650--700 ℃. These processes caused local variations of water and alkali activity in the fluids, resulting in various mineral assemblages within the dehydration zone. The petrological observations are substantiated by experiments on the interaction of the Sand River gneiss with the H2O-CO2-（K, Na）Cl fluids at 750 and 800 ℃ and 5.5 kbar. It follows that the interaction of biotite-amphibole gneiss with H2O-CO2-（K, Na）CI fluids is accompanied by partial melting at 750--800 ℃. Orthopyroxene-bearing assemblages are characteristic for temperature 800 ℃ and are stable in equilibrium with fluids with low salt concentrations, while salt-rich fluids produce clinopyroxene-bearing assemblages. These observations are in good agreement with the petrological data on the dehydration zones within the Sand River olthogneisses.展开更多
The SW96 formulation explicit in Helmholtz free energy proposed by Span and Wagner(1996)is the most accurate multifunction equation of state of CO_2 fluid,from which all thermodynamic properties can be obtained over a...The SW96 formulation explicit in Helmholtz free energy proposed by Span and Wagner(1996)is the most accurate multifunction equation of state of CO_2 fluid,from which all thermodynamic properties can be obtained over a wide temperature-pressure range from 216.592 to 1100 K and from 0 to 8000 bar with or close to experimental accuracy.This paper reports the applications of the SW96 formulation in fluid inclusions and mineral-fluid equilibria.A reliable and highly efficient algorithm is presented for the saturated properties of CO_2 so that the formulation can be conveniently applied in the study of fluid inclusions,such as calculation of homogenization pressures,homogenization densities(or molar volumes),volume fractions of vapor phase and isochores.Meanwhile,the univariant curves of some typical decarbonation reactions of minerals are calculated with the SW96 formulation and relevant thermodynamic models of minerals.The computer code of the SW96 formulation can be obtained from the corresponding author.展开更多
Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandston...Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandstone is characterized by double injection of CO_(2)and oil-gas in the Jiyang Depression that have experienced a relatively complex diagenetic fluid evolution process.The diagenetic sequence of secondary minerals involves secondary enlargement of quartz,kaolinite,first-stage calcite,dawsonite,second-stage calcite,ferrocalcite,dolomite and ankerite.Hydrocarbon charging in the dawsonite-bearing sandstone occurred at around 2.6–0 Myr.The CO_(2)charging event occurred during Dongying tectonism,forming the Pingfangwang CO_(2)gas reservoir,which provided an abundant carbon source for dawsonite precipitation.Carbon and oxygen isotopic compositions of dawsonite demonstrate that CO_(2)forming the dawsonite was of an inorganic origin derived from the mantle,and that water mediating the proc-ess during dawsonite precipitation was sequestered brine with a fluid temperature of 82℃.The evolutionary sequence of the diagenetic fluid in the dawsonite-bearing sandstone was:alkaline syngenetic fluids,weak alkaline fluids during organic acid forma-tion,acidic fluids in the early stage of CO_(2)injection,alkaline fluids in the late stage of CO_(2)injection,and weak alkaline fluids during oil and gas charging.The mode indicates an increase in-HCO_(3)because of the CO_(2)injection,and the loss of Ca^(2+)and Mg^(2+)due to the precipitation of carbonate minerals.Therefore,the evolutionary mode of diagenetic fluids is in good agreement with high HCO_(3)^(-),low Ca^(2+)and low Mg^(2+)composition of the present formation water in the dawsonite-bearing sandstone.展开更多
In this paper some new advances in the study of fluid inclusions of the Yinshan deposit in Jiangxi Province, China, are presented. The fluid inclusions of the deposit can be divided into four types: 1) gas rich inclus...In this paper some new advances in the study of fluid inclusions of the Yinshan deposit in Jiangxi Province, China, are presented. The fluid inclusions of the deposit can be divided into four types: 1) gas rich inclusions; 2) liquid rich inclusions; 3) salt saturated H 2O inclusions; and 4) single phase or multiphase CO 2 rich inclusions. Homogenization temperatures of the fluid inclusions range from 100 to 520℃, mainly in the range 120-400℃. The daughter crystal bearing multiphase inclusions present in quartz porphyries (including Nos. 13 and 4 dikes) have been observed. In ore veins, some daughter crystal bearing multiphase inclusions have been observed, too. On the basis of the results of fluid inclusion research, the authors suggest that the ore forming fluid must have a close genetic relation to magmatic hydrothermal solution. The ore forming fluid was dominantly originated from the depth and the mixing of magmatic solution with meteoric water was enhanced during ascending of the fluid, accompanying immiscibility and boiling of fluid. There may be a concealed igneous body at the depth of the Yinshan deposit, which furnishes the scientific basis for metallogenic prognosis at the depth of the Yinshan deposit.展开更多
Raman peaks of various hydrates in the H20-NaCl-CaCl2 system have been previously identified, but a quantitative relationship between the Raman peaks and XNaCl （i.e.,NaCl/ （NaCl＋CaCl2）） has not been established, ...Raman peaks of various hydrates in the H20-NaCl-CaCl2 system have been previously identified, but a quantitative relationship between the Raman peaks and XNaCl （i.e.,NaCl/ （NaCl＋CaCl2）） has not been established, mainly due to the difficulty to freeze the solutions. This problem was solved by adding alumina powder to the solutions to facilitate nucleation of crystals. Cryogenic （-185℃） Raman spectroscopic studies of alumina-spiced solutions indicate that XNaCl is linearly correlated with the total peak area fraction of hydrohalite. Capsules of solutions made from silica capillary were prepared to simulate fluid inclusions. Most of these artificial fluid inclusions could not be totally frozen even at temperatures as low as -185℃, and the total peak area fraction of hydrohalite is not correlated linearly with XNaCI. However, the degree of deviation （△XNaCl） from the linear correlation established earlier is related to the amount of residual solution, which is reflected by the ratio （r） of the baseline ＂bump＂ area, resulting from the interstitial unfrozen brine near 3435 cm^-1, and the total hydrate peak area between 3350 and 3600 cm^-1. A linear correlation between △XNaCl and r is established to estimate XNaCl from cryogenic Raman spectroscopic analysis for fluid inclusions.展开更多
Qiongdongnan Basin has a tectonic geological background of high temperature and high pressure in a deep reservoir setting,with mantle-derived CO2.A water-rock reaction device was used under high temperature and high p...Qiongdongnan Basin has a tectonic geological background of high temperature and high pressure in a deep reservoir setting,with mantle-derived CO2.A water-rock reaction device was used under high temperature and high pressure conditions,in conjunction with scanning electron microscope(SEM)observations,to carry out an experimental study of the diagenetic reaction between sandstone at depth and CO2-rich fluid,which is of great significance for revealing the dissolution of deep clastic rock reservoirs and the developmental mechanism of secondary pores,promoting deep oil and gas exploration.In this study,the experimental scheme of the water-rock reaction system was designed according to the parameters of the diagenetic background of the deep sandstone reservoir in the Qiongdongnan Basin.Three groups of single mineral samples were prepared in this experiment,including K-feldspar samples,albite samples and calcite samples.Using CO2 as a reaction solution,a series of diagenetic reaction simulation experiments were carried out in a semi-closed high temperature and high pressure simulation system.A field emission scanning electron microscope(SEM)was used to observe the microscopic appearance of the mineral samples after the water-rock reaction,the characteristics of dissolution under high temperature and high pressure,as well as the development of secondary pores.The experimental results showed that the CO2-rich fluid has an obvious dissolution effect on K-feldspar,albite and calcite under high temperature and high pressure.For the three minerals,the main temperature and pressure window for dissolution ranged from 150℃to 300℃and 45 MPa to 60 MPa.Scanning electron microscope observations revealed that the dissolution effect of K-feldspar is most obvious under conditions of 150℃and 45 MPa,in contrast to conditions of200℃and 50 MPa for albite and calcite.Through the comparative analysis of experimental conditions and procedures,a coupling effect occurred between the temperature and pressure change and the dissolution strength and calcite.Under high temperature and high pressure,pressure changed the solubility of CO2,furthermore,the dissolution effect and strength of the sandstone components were also affected.The experiment revealed that high temperature and high pressure conditions with CO2-rich fluid has a significant dissolution effect on aluminosilicate minerals and is conducive to the formation of secondary pores and effective reservoirs.Going forward with the above understanding has important implications for the promotion of deep oil and gas exploration.展开更多
The carbon isotopic composition of CO_(2)inclusions trapped in minerals reflects the origin and evolution of CO_(2)-bearing fluids and melts,and records the multiple-stages carbon geodynamic cycle,as CO_(2)took part i...The carbon isotopic composition of CO_(2)inclusions trapped in minerals reflects the origin and evolution of CO_(2)-bearing fluids and melts,and records the multiple-stages carbon geodynamic cycle,as CO_(2)took part in various geological processes widely.However,the practical method for determination isotope composition of individual CO_(2)inclusion is still lacking.Developing a microanalytical technique with spatial resolution in micrometers to precisely determinate theδ^(13)C value of individual CO_(2)inclusion,will make it possible to analyze a tiny portion of a zoning mineral crystal,distinguish the differences in micro-scale,and possible to find many useful information that could not be obtained with the bulk extraction and analysis techniques.In this study,we systematically collected Raman spectra of CO_(2)standards with different d13C values(34.9‰to 3.58‰)at 32.0℃and from 7.0 MPa to 120.0 MPa,and developed a new procedure to precisely determinate theδ^(13)C value of individual CO_(2)inclusion.We investigated the relationship among the Raman peak intensity ratio,d13C value,and CO_(2)density,and established a calibration model with high accuracy(0.5‰1.5‰),sufficient for geological application to distinguish different source of CO_(2)with varyingδ^(13)CO_(2).As a demonstration,we measured theδ^(13)C values and the density of CO_(2)inclusions in the growth zones of alkali basalt-hosted corundum megacrysts from Changle,Shandong Province.We found the significant differences of density and d13C between the CO_(2)inclusions in the core of corundum and those inclusions in the outer growth zones,the d13C value decreases from core to rim with decreasing density:δ^(13)C values are from7.5‰to9.2‰for the inclusions in the core,indicating the corundum core was crystallized from mantle-derived magmas;from13.5‰to18.5‰for CO_(2)inclusions in zone 1 and from16.5‰to–22.0‰for inclusions in zone 2,indicating the outer zones of corundum grew in a lowδ^(13)C value environment,resulted from an infilling of low d13C value fluid and/or degassing of the ascending basaltic magma.展开更多
文摘We first report discovery of the spinel-garnet-orthopyroxene granulite with pure CO2 fluid inclusions from the Fuyun region of the late Paleozoic Altay orogenic belt in Central Asia, NW China. The rock is characterized by an assemblage of garnet, orthopyroxene, spinel, cordierite, biotite, plagioclase and quartz. Symplectites of orthopyroxene and spinel, and orthopyroxene and cordierite indicate decompression under UHT conditions. Mineral chemistry shows that the or-thopyroxenes have high XMg and A12O3 contents (up to 9.23 wt%). Biotites are enriched in TiO2 and XMg and are stable under granulite facies conditions. The garnet and quartz from the rock carry monophase fluid inclusions which show peak melting temperatures of around -56.7℃, indicating a pure CO2 species being presented during the ultrahigh-T metamorphism in the Altay orogenic belt. The inclusions homogenize into a liquid phase at temperatures around 15.3-23.8℃ translating into CO2 densities of the order of 0.86-0.88 g/cm3. Based on preliminary mineral paragenesis, reaction textures and petrogenetic grid considerations, we infer that the rock was subjected to UHT conditions. The CO2-rich fluids were trapped during exhumation along a clockwise P-T path following isothermal decompression under UHT conditions.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.41922023 and 41830425)the Fundamental Research Funds for the Central Universities(Grant Nos.020614380056 and 020614380078).
文摘We re-evaluate the Raman spectroscopic quantification of the molar ratio and pressure for CH4–CO2 mixtures.Firstly,the Raman quantification factors of CH4 and CO2 increase with rising pressure at room temperature,indicating that Raman quantification of CH4/CO2 molar ratio can be applied to those fluid inclusions(FIs)with high internal pressure(i.e.,>15 MPa).Secondly,the v1(CH4)peak position shifts to lower wavenumber with increasing pressure at constant temperature,confirming that the v1(CH4)peak position can be used to calculate the fluid pressure.However,this method should be carefully calibrated before applying to FI analyses because large discrepancies exist among the reported v1(CH4)-P curves,especially in the highpressure range.These calibrations are applied to CH4-rich FIs in quartz veins of the Silurian Longmaxi black shales in southern Sichuan Basin.The vapor phases of these FIs are mainly composed of CH4 and minor CO2,with CO2 molar fractions from4.4%to 7.4%.The pressure of single-phase gas FI ranges from 103.65 to 128.35 MPa at room temperature,which is higher than previously reported.Thermodynamic calculations supported the presence of extremely high-pressure CH4-saturated fluid(218.03–256.82 MPa at 200°C),which may be responsible for the expulsion of CH4 to adjacent reservoirs.
文摘Previous cryogenic Raman spectroscopic analysis of H_2O-NaCl-CaCl_2 solutions has identified the Raman peaks of various hydrates of NaCl and CaCl_2,and established a linear relationship between Raman band intensity of the hydrates and the composition of the solution（NaCl/（NaCl＋CaCl_2） molar ratio,or X_（NaC1）） using synthetic fluids,which created the opportunity to quantitatively determine the solute composition of aqueous fluid inclusions with cryogenic Raman spectroscopy.This paper aims to test the feasibility of this newly established method with natural fluid inclusions.Twenty-five fluid inclusions in quartz from various occurrences which show a high degree of freezing during the cooling processes were carefully chosen for cryogenic Raman analysis.X_（Na）Cl was calculated using their spectra and an equation established in a previous study.These inclusions were then analyzed with the thermal decrepitation-SEM-EDS method.The X_（NaCl） values estimated from the two methods show a 1：1 correlation,indicating that the new,non-destructive cryogenic Raman spectroscopic analysis method can indeed be used for fluid inclusion compositional study.
文摘The density of CO<sub>2</sub> inclusions in minerals is commonly used to determine the crystallizing conditions of the host minerals.However,the conventional microthermometry method is difficult to apply for inclusions that are small in size（【5-10μm） or low in density.Raman analysis is an alternative method for determining CO<sub>2</sub> density,provided that
基金Supported by NSFC project No. 40372066 and SRFDP No. 20030183042
文摘Methane-rich fluids were recognized to be hosted in the reservoir volcanic rocks as primary inclusions. Samples were collected from core-drillings of volcanic gas reservoirs with reversed δ13C of alkane in the Xujiaweizi depression of the Songliao Basin. The volcanic rocks are rhyolite dominant being enriched in the more incompatible elements like Cs, Rb, Ba, Th, U and Th with relative high LREE, depleted HREE and negative anomalies of Ti and Nb, suggesting a melt involving both in mantle source and crustal assimilation. Primary fluids hosted in the volcanic rocks should have the same provenance with the magma. The authors concluded that the enclosed CH4 in the volcanics are mantle/magma-derived alkane and the reversed δ13C of alkane in the corresponding gas reservoirs is partly resulted from mixture between biogenic and abiogenic gases.
文摘Comparing compositions of the fluid inclusions in volcanic rocks to the contents and isotopes of the gases in corresponding volcanic reservoirs using microthermometry, Raman microspectroscopy and mass spectrum analysis, we found that： （1） up to 82 mole% methane exists in the primary inclusions hosted in the reservoir volcanic rocks; （2） high CH4 inclusions recognized in the volcanic rocks correspond to CH4-bcaring CO2 reservoirs that are rich in helium and with a high ^3He/^4He ratio and which show reversed order of 813C in alkane; （3） in gas reservoirs of such abiotic methane （〉80%） and a mix of CH4 and CO2, the enclosed content of CH4 in the volcanic inclusions is usually below 42 mole%, and the reversed order of δ^13C in alkane is sometimes irregular in the corresponding gas pools; （4） a glassy inclusion with a homogeneous temperature over 900℃ also contains a small portion of CH4 although predominantly CO2. This affinity between gas pool and content of inclusion in the same volcanic reservoirs demonstrates that magma-originated gases, both CH4 and CO2, have contributed significantly to the corresponding gas pools and that the assumed hydrocarbon budget of the bulk earth might be much larger than conventionally supposed.
基金supported by Russian Foundation for Basic Research(project 10-05-00040 to OGS)Russian President Grants for Young Scientists(MD-222.2012.5 to OGS)+1 种基金grant from the National Science Foundation of South Africa(GUN:20531 92 to DDvR)University of Johannesburg as a part of the Russian South African scientific collaboration
文摘Reaction textures and fluid inclusions in the -2.0 Ga pyroxene-bearing dehydration zones within the Sand River biotite-hornblende orthogneisses （Central Zone of the Limpopo Complex） suggest that the formation of these zones is a result of close interplay between dehydration process along ductile shear zones triggered by H2O-CO2-salt fluids at 750--800 ℃ and 5.5--6.2 kbar, partial melting, and later exsolution of residual brine and H2O-CO2 fluids during melt crystallization at 650--700 ℃. These processes caused local variations of water and alkali activity in the fluids, resulting in various mineral assemblages within the dehydration zone. The petrological observations are substantiated by experiments on the interaction of the Sand River gneiss with the H2O-CO2-（K, Na）Cl fluids at 750 and 800 ℃ and 5.5 kbar. It follows that the interaction of biotite-amphibole gneiss with H2O-CO2-（K, Na）CI fluids is accompanied by partial melting at 750--800 ℃. Orthopyroxene-bearing assemblages are characteristic for temperature 800 ℃ and are stable in equilibrium with fluids with low salt concentrations, while salt-rich fluids produce clinopyroxene-bearing assemblages. These observations are in good agreement with the petrological data on the dehydration zones within the Sand River olthogneisses.
基金jointly supported by the National Natural Science Foundation of China(Grant No.41673065)the National Key Basic Research Development Program(Grant No.2015CB452606)
文摘The SW96 formulation explicit in Helmholtz free energy proposed by Span and Wagner(1996)is the most accurate multifunction equation of state of CO_2 fluid,from which all thermodynamic properties can be obtained over a wide temperature-pressure range from 216.592 to 1100 K and from 0 to 8000 bar with or close to experimental accuracy.This paper reports the applications of the SW96 formulation in fluid inclusions and mineral-fluid equilibria.A reliable and highly efficient algorithm is presented for the saturated properties of CO_2 so that the formulation can be conveniently applied in the study of fluid inclusions,such as calculation of homogenization pressures,homogenization densities(or molar volumes),volume fractions of vapor phase and isochores.Meanwhile,the univariant curves of some typical decarbonation reactions of minerals are calculated with the SW96 formulation and relevant thermodynamic models of minerals.The computer code of the SW96 formulation can be obtained from the corresponding author.
基金supported by the National Natural Science Foundation of China(Nos.42072130,41872152).
文摘Based on the petrology,isotope geochemistry and fluid inclusions analysis,we established the evolutionary mode of the diagenetic fluid of dawsonite-bearing sandstone in the Jiyang Depression.Dawsonite-bearing sandstone is characterized by double injection of CO_(2)and oil-gas in the Jiyang Depression that have experienced a relatively complex diagenetic fluid evolution process.The diagenetic sequence of secondary minerals involves secondary enlargement of quartz,kaolinite,first-stage calcite,dawsonite,second-stage calcite,ferrocalcite,dolomite and ankerite.Hydrocarbon charging in the dawsonite-bearing sandstone occurred at around 2.6–0 Myr.The CO_(2)charging event occurred during Dongying tectonism,forming the Pingfangwang CO_(2)gas reservoir,which provided an abundant carbon source for dawsonite precipitation.Carbon and oxygen isotopic compositions of dawsonite demonstrate that CO_(2)forming the dawsonite was of an inorganic origin derived from the mantle,and that water mediating the proc-ess during dawsonite precipitation was sequestered brine with a fluid temperature of 82℃.The evolutionary sequence of the diagenetic fluid in the dawsonite-bearing sandstone was:alkaline syngenetic fluids,weak alkaline fluids during organic acid forma-tion,acidic fluids in the early stage of CO_(2)injection,alkaline fluids in the late stage of CO_(2)injection,and weak alkaline fluids during oil and gas charging.The mode indicates an increase in-HCO_(3)because of the CO_(2)injection,and the loss of Ca^(2+)and Mg^(2+)due to the precipitation of carbonate minerals.Therefore,the evolutionary mode of diagenetic fluids is in good agreement with high HCO_(3)^(-),low Ca^(2+)and low Mg^(2+)composition of the present formation water in the dawsonite-bearing sandstone.
文摘In this paper some new advances in the study of fluid inclusions of the Yinshan deposit in Jiangxi Province, China, are presented. The fluid inclusions of the deposit can be divided into four types: 1) gas rich inclusions; 2) liquid rich inclusions; 3) salt saturated H 2O inclusions; and 4) single phase or multiphase CO 2 rich inclusions. Homogenization temperatures of the fluid inclusions range from 100 to 520℃, mainly in the range 120-400℃. The daughter crystal bearing multiphase inclusions present in quartz porphyries (including Nos. 13 and 4 dikes) have been observed. In ore veins, some daughter crystal bearing multiphase inclusions have been observed, too. On the basis of the results of fluid inclusion research, the authors suggest that the ore forming fluid must have a close genetic relation to magmatic hydrothermal solution. The ore forming fluid was dominantly originated from the depth and the mixing of magmatic solution with meteoric water was enhanced during ascending of the fluid, accompanying immiscibility and boiling of fluid. There may be a concealed igneous body at the depth of the Yinshan deposit, which furnishes the scientific basis for metallogenic prognosis at the depth of the Yinshan deposit.
基金supported by an NSERC-Discovery grant(to Chi)in part by the Knowledge Innovation Program of Chinese Academy of Sciences(SIDSSE201302)
文摘Raman peaks of various hydrates in the H20-NaCl-CaCl2 system have been previously identified, but a quantitative relationship between the Raman peaks and XNaCl （i.e.,NaCl/ （NaCl＋CaCl2）） has not been established, mainly due to the difficulty to freeze the solutions. This problem was solved by adding alumina powder to the solutions to facilitate nucleation of crystals. Cryogenic （-185℃） Raman spectroscopic studies of alumina-spiced solutions indicate that XNaCl is linearly correlated with the total peak area fraction of hydrohalite. Capsules of solutions made from silica capillary were prepared to simulate fluid inclusions. Most of these artificial fluid inclusions could not be totally frozen even at temperatures as low as -185℃, and the total peak area fraction of hydrohalite is not correlated linearly with XNaCI. However, the degree of deviation （△XNaCl） from the linear correlation established earlier is related to the amount of residual solution, which is reflected by the ratio （r） of the baseline ＂bump＂ area, resulting from the interstitial unfrozen brine near 3435 cm^-1, and the total hydrate peak area between 3350 and 3600 cm^-1. A linear correlation between △XNaCl and r is established to estimate XNaCl from cryogenic Raman spectroscopic analysis for fluid inclusions.
基金supported financially by the National Science and Technology Major Project of the Ministry of Science and Technology of China(Grant No.2016ZX05026-007-005)。
文摘Qiongdongnan Basin has a tectonic geological background of high temperature and high pressure in a deep reservoir setting,with mantle-derived CO2.A water-rock reaction device was used under high temperature and high pressure conditions,in conjunction with scanning electron microscope(SEM)observations,to carry out an experimental study of the diagenetic reaction between sandstone at depth and CO2-rich fluid,which is of great significance for revealing the dissolution of deep clastic rock reservoirs and the developmental mechanism of secondary pores,promoting deep oil and gas exploration.In this study,the experimental scheme of the water-rock reaction system was designed according to the parameters of the diagenetic background of the deep sandstone reservoir in the Qiongdongnan Basin.Three groups of single mineral samples were prepared in this experiment,including K-feldspar samples,albite samples and calcite samples.Using CO2 as a reaction solution,a series of diagenetic reaction simulation experiments were carried out in a semi-closed high temperature and high pressure simulation system.A field emission scanning electron microscope(SEM)was used to observe the microscopic appearance of the mineral samples after the water-rock reaction,the characteristics of dissolution under high temperature and high pressure,as well as the development of secondary pores.The experimental results showed that the CO2-rich fluid has an obvious dissolution effect on K-feldspar,albite and calcite under high temperature and high pressure.For the three minerals,the main temperature and pressure window for dissolution ranged from 150℃to 300℃and 45 MPa to 60 MPa.Scanning electron microscope observations revealed that the dissolution effect of K-feldspar is most obvious under conditions of 150℃and 45 MPa,in contrast to conditions of200℃and 50 MPa for albite and calcite.Through the comparative analysis of experimental conditions and procedures,a coupling effect occurred between the temperature and pressure change and the dissolution strength and calcite.Under high temperature and high pressure,pressure changed the solubility of CO2,furthermore,the dissolution effect and strength of the sandstone components were also affected.The experiment revealed that high temperature and high pressure conditions with CO2-rich fluid has a significant dissolution effect on aluminosilicate minerals and is conducive to the formation of secondary pores and effective reservoirs.Going forward with the above understanding has important implications for the promotion of deep oil and gas exploration.
基金supported by National Nature Science Foundation of China(92058208)the National Key Research and Development Program of China(2018YFC0310006-04).
文摘The carbon isotopic composition of CO_(2)inclusions trapped in minerals reflects the origin and evolution of CO_(2)-bearing fluids and melts,and records the multiple-stages carbon geodynamic cycle,as CO_(2)took part in various geological processes widely.However,the practical method for determination isotope composition of individual CO_(2)inclusion is still lacking.Developing a microanalytical technique with spatial resolution in micrometers to precisely determinate theδ^(13)C value of individual CO_(2)inclusion,will make it possible to analyze a tiny portion of a zoning mineral crystal,distinguish the differences in micro-scale,and possible to find many useful information that could not be obtained with the bulk extraction and analysis techniques.In this study,we systematically collected Raman spectra of CO_(2)standards with different d13C values(34.9‰to 3.58‰)at 32.0℃and from 7.0 MPa to 120.0 MPa,and developed a new procedure to precisely determinate theδ^(13)C value of individual CO_(2)inclusion.We investigated the relationship among the Raman peak intensity ratio,d13C value,and CO_(2)density,and established a calibration model with high accuracy(0.5‰1.5‰),sufficient for geological application to distinguish different source of CO_(2)with varyingδ^(13)CO_(2).As a demonstration,we measured theδ^(13)C values and the density of CO_(2)inclusions in the growth zones of alkali basalt-hosted corundum megacrysts from Changle,Shandong Province.We found the significant differences of density and d13C between the CO_(2)inclusions in the core of corundum and those inclusions in the outer growth zones,the d13C value decreases from core to rim with decreasing density:δ^(13)C values are from7.5‰to9.2‰for the inclusions in the core,indicating the corundum core was crystallized from mantle-derived magmas;from13.5‰to18.5‰for CO_(2)inclusions in zone 1 and from16.5‰to–22.0‰for inclusions in zone 2,indicating the outer zones of corundum grew in a lowδ^(13)C value environment,resulted from an infilling of low d13C value fluid and/or degassing of the ascending basaltic magma.
