Three-phase NaCl-H_2O fluid inclusions featuring halite dissolution temperature（Tm）higher than vapor bubble disappearance temperature（T_h） are commonly observed in porphyry copper/molybdenum deposits,skarn-type de...Three-phase NaCl-H_2O fluid inclusions featuring halite dissolution temperature（Tm）higher than vapor bubble disappearance temperature（T_h） are commonly observed in porphyry copper/molybdenum deposits,skarn-type deposits and other magmatic- hydrothermal ore deposits.Based on ｜ΔV_1｜（the absolute value of volume variation of NaCl-H_2O solution in a heating or cooling process of inclusions）= ｜ΔV_s｜（the absolute value of volume variation of the halite crystal in a heating or cooling process of inclusions） and on the principle of conservation of the mass of NaCl and H_2O,we systematically calculated the densities of NaCl-H_2O solutions in the solid-liquid two-phase field for temperatures（T_h） from 0.1℃ to 800℃ and salinities from 26.3 wt%to 99.2wt%.Consequently for the first time we obtained the upper limit of the density of NaCI-H_2O solutions in the solid-liquid twophase field for T_b〈T_m inclusions with variant salinities.The results indicate that for inclusions of the T_h〈T_m type with the same T_h,the higher the T_m or salinity is,the higher the density of the NaClsaturated solution will be.If a group of fluid inclusions were homogeneously trapped,they must have the same T_h value and the same T_m or salinity value.This may be used to distinguish homogeneous,inhomogeneous,and multiple entrapments of fluid inclusions.展开更多
The composition of fluid inclusions in the H_2O-NaCl-CaCl_2 system has been generally graphically estimated using the melting temperatures of hydrohalite(T_(m-HH))and ice(T_(m-ice)).Here we present two equations that ...The composition of fluid inclusions in the H_2O-NaCl-CaCl_2 system has been generally graphically estimated using the melting temperatures of hydrohalite(T_(m-HH))and ice(T_(m-ice)).Here we present two equations that can be used to calculate the relative proportion of NaCl(i.e.,NaCl/[NaCl+CaCl_2],or X_(NaCl))and the total salinity( i.e.,NaC1 + CaC12,wt% )for fluid inclusions with ice as the last melting phase.X_(NaCl)can be calculated from T_(m-HH)using the following equation: y=(a+bx)^(-1/c) where y is X_(NaCl),x is T_(m-HH),a=0.33124402,b=-0.031518028,and c=0.22932736.In the cases where only T_(m-ice)is measured and T_(m-HH)is not known,T_(m-ice)can be used as the maximum possible TIn.nil to calculate the maximum value of X_(NaCl)using the above equation.In these cases,the following equation can be used to calculate the maximum total salinity: y=(a+bx+cx^2)^(-1) where y is salinity,x is T_(m-HH),a=0.057184817,b=0.00078565757,and c=5.7262766E-6.Because the isothems in the field of ice are sub-parallel to the NaCl-CaCl_2 binary side in the H20-NaC1-CaC12 ternary system,the errors in salinity calculation introduced by the above approximation are small(less than 2 wt% ).A Windows program for calculation of X_(NsCl)and salinity is available at: http://uregina.ca/~chiguox.展开更多
To study the feasibility of CO2 geological sequestration,it is needed to understand the complicated mul- tiple-phase equilibrium and the densities of aqueous solution with CO2 and multi-ions under wide geological cond...To study the feasibility of CO2 geological sequestration,it is needed to understand the complicated mul- tiple-phase equilibrium and the densities of aqueous solution with CO2 and multi-ions under wide geological condi- tions(273.15—473.15K,0—60MPa),which are also essential for designing separation equipments in chemical or oil-related industries.For this purpose,studies on the relevant phase equilibria and densities are reviewed and ana- lyzed and the method to improve or modify the existing model is suggested in order to obtain more reliable pre- dictions in a wide temperature and pressure range.Besides,three different models(the electrolyte non random two-liquid(ELECNRTL),the electrolyte NRTL combining with Helgeson model(ENRTL-HG),Pitzer activity co- efficient model combining with Helgeson model(PITZ-HG))are used to calculate the vapor-liquid phase equilib- rium of CO2-H2O and CO2-H2O-NaCl systems.For CO2-H2O system,the calculation results agree with the experi- mental data very well at low and medium pressure(0—20MPa),but there are great discrepancies above 20MPa.For the water content at 473.15K,the calculated results agree with the experimental data quite well.For the CO2-H2O-NaCl system,the PITZ-HG model show better results than ELECNRTL and ENRTL-HG models at the NaCl concentration of 0.52mol·L -1 .Bur for the NaCl concentration of 3.997mol·L -1 ,using the ELECNRTL and ENRTL-HG models gives better results than using the PITZ-HG model.It is shown that available experimental data and the thermodynamic calculations can satisfy the needs of the calculation of the sequestration capacity in the temperature and pressure range for disposal of CO2 in deep saline aquifers.More experimental data and more accu- rate thermodynamic calculations are needed in high temperature and pressure ranges(above 398.15K and 31.5MPa).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
Salt-hydrates have diagnostic cryogenic Raman spectra, which can reflect the composition of the parent solutions. As analogue to the natural fluid inclusions, the synthetic inclusions can be used to validate numerous ...Salt-hydrates have diagnostic cryogenic Raman spectra, which can reflect the composition of the parent solutions. As analogue to the natural fluid inclusions, the synthetic inclusions can be used to validate numerous assumptions related to fluid inclu- sion research. They can also be used to test the feasibility of application of laser Raman spectroscopy to individual fluid inclusion analysis. Using the tech- nique proposed by Sterner and Bodnar(1984), syn- thetic inclusions of the systems H2O and NaCl-H2O (with NaCl as 5.12 wt%, 9.06 wt%, 16.6 wt% and 25 wt%) were formed under the pressures from 50Mpa to 100Mpa and at the temperatures from 500℃ to 600℃. In situ cryogenic Raman spectra were col- lected at about –180℃ by combined use of freezing- heating stage and Laser Raman Microscopy. It is shown that hydrohalite (NaCl?2H2O), the salt-hydrate of NaCl in the fluid inclusions has the specific Raman spectrum and can be used as the standard to verify the existence of NaCl in the aqueous inclusions. The crystalline ice other than amorphous ice (glasses) formed from the aqueous phase whthin the synthetic inclusions during the initial freezing, but hydrohalite did not form. Subsequent warming of these inclusions induced a phase change, typically between ap- proximately –40 and –22℃, that represents the hy- drohalite crystallization event but not a eutectic melting event. So, for fluid inclusions in the system NaCl-H2O, interpretation of phase behavior below the eutectic temperature (–20.8℃) should be made with caution. The ratios of the relative intensity and the area of Raman spectra between 3423 cm–1 peak of hydrohalite and 3098 cm–1 peak of ice show positivecorrelations to the salinities in aqueous inclusions, which can be used to determine the salinity of NaCl- H2O system inclusions.展开更多
基金supported by China National Natural Science Foundation(No.4997032)the Basic Business Fee Special Foundation for Chinese central nonprofit research institutes(K0710)
文摘Three-phase NaCl-H_2O fluid inclusions featuring halite dissolution temperature（Tm）higher than vapor bubble disappearance temperature（T_h） are commonly observed in porphyry copper/molybdenum deposits,skarn-type deposits and other magmatic- hydrothermal ore deposits.Based on ｜ΔV_1｜（the absolute value of volume variation of NaCl-H_2O solution in a heating or cooling process of inclusions）= ｜ΔV_s｜（the absolute value of volume variation of the halite crystal in a heating or cooling process of inclusions） and on the principle of conservation of the mass of NaCl and H_2O,we systematically calculated the densities of NaCl-H_2O solutions in the solid-liquid two-phase field for temperatures（T_h） from 0.1℃ to 800℃ and salinities from 26.3 wt%to 99.2wt%.Consequently for the first time we obtained the upper limit of the density of NaCI-H_2O solutions in the solid-liquid twophase field for T_b〈T_m inclusions with variant salinities.The results indicate that for inclusions of the T_h〈T_m type with the same T_h,the higher the T_m or salinity is,the higher the density of the NaClsaturated solution will be.If a group of fluid inclusions were homogeneously trapped,they must have the same T_h value and the same T_m or salinity value.This may be used to distinguish homogeneous,inhomogeneous,and multiple entrapments of fluid inclusions.
文摘The composition of fluid inclusions in the H_2O-NaCl-CaCl_2 system has been generally graphically estimated using the melting temperatures of hydrohalite(T_(m-HH))and ice(T_(m-ice)).Here we present two equations that can be used to calculate the relative proportion of NaCl(i.e.,NaCl/[NaCl+CaCl_2],or X_(NaCl))and the total salinity( i.e.,NaC1 + CaC12,wt% )for fluid inclusions with ice as the last melting phase.X_(NaCl)can be calculated from T_(m-HH)using the following equation: y=(a+bx)^(-1/c) where y is X_(NaCl),x is T_(m-HH),a=0.33124402,b=-0.031518028,and c=0.22932736.In the cases where only T_(m-ice)is measured and T_(m-HH)is not known,T_(m-ice)can be used as the maximum possible TIn.nil to calculate the maximum value of X_(NaCl)using the above equation.In these cases,the following equation can be used to calculate the maximum total salinity: y=(a+bx+cx^2)^(-1) where y is salinity,x is T_(m-HH),a=0.057184817,b=0.00078565757,and c=5.7262766E-6.Because the isothems in the field of ice are sub-parallel to the NaCl-CaCl_2 binary side in the H20-NaC1-CaC12 ternary system,the errors in salinity calculation introduced by the above approximation are small(less than 2 wt% ).A Windows program for calculation of X_(NsCl)and salinity is available at: http://uregina.ca/~chiguox.
基金Supported by the Chinese National Science Foundation for 0utstanding Young Scholars （No.29925616）, the Joint Research Fund for Young Scholars in Hong Kong and Abroad （No.20428606）, the National Natural Science Foundation of China （Nos.20236010, 20246002, 20376032）, the Natural Science Foundation of Jiangsu Province （Nos.BK2002016, BK2004215） and Chinese National Fundamental Research Development Program （973 Program： 2003CB615700）.
文摘To study the feasibility of CO2 geological sequestration,it is needed to understand the complicated mul- tiple-phase equilibrium and the densities of aqueous solution with CO2 and multi-ions under wide geological condi- tions(273.15—473.15K,0—60MPa),which are also essential for designing separation equipments in chemical or oil-related industries.For this purpose,studies on the relevant phase equilibria and densities are reviewed and ana- lyzed and the method to improve or modify the existing model is suggested in order to obtain more reliable pre- dictions in a wide temperature and pressure range.Besides,three different models(the electrolyte non random two-liquid(ELECNRTL),the electrolyte NRTL combining with Helgeson model(ENRTL-HG),Pitzer activity co- efficient model combining with Helgeson model(PITZ-HG))are used to calculate the vapor-liquid phase equilib- rium of CO2-H2O and CO2-H2O-NaCl systems.For CO2-H2O system,the calculation results agree with the experi- mental data very well at low and medium pressure(0—20MPa),but there are great discrepancies above 20MPa.For the water content at 473.15K,the calculated results agree with the experimental data quite well.For the CO2-H2O-NaCl system,the PITZ-HG model show better results than ELECNRTL and ENRTL-HG models at the NaCl concentration of 0.52mol·L -1 .Bur for the NaCl concentration of 3.997mol·L -1 ,using the ELECNRTL and ENRTL-HG models gives better results than using the PITZ-HG model.It is shown that available experimental data and the thermodynamic calculations can satisfy the needs of the calculation of the sequestration capacity in the temperature and pressure range for disposal of CO2 in deep saline aquifers.More experimental data and more accu- rate thermodynamic calculations are needed in high temperature and pressure ranges(above 398.15K and 31.5MPa).
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.
基金supported by National Natural Science Foundation of China(Grant No.40221301).
文摘Salt-hydrates have diagnostic cryogenic Raman spectra, which can reflect the composition of the parent solutions. As analogue to the natural fluid inclusions, the synthetic inclusions can be used to validate numerous assumptions related to fluid inclu- sion research. They can also be used to test the feasibility of application of laser Raman spectroscopy to individual fluid inclusion analysis. Using the tech- nique proposed by Sterner and Bodnar(1984), syn- thetic inclusions of the systems H2O and NaCl-H2O (with NaCl as 5.12 wt%, 9.06 wt%, 16.6 wt% and 25 wt%) were formed under the pressures from 50Mpa to 100Mpa and at the temperatures from 500℃ to 600℃. In situ cryogenic Raman spectra were col- lected at about –180℃ by combined use of freezing- heating stage and Laser Raman Microscopy. It is shown that hydrohalite (NaCl?2H2O), the salt-hydrate of NaCl in the fluid inclusions has the specific Raman spectrum and can be used as the standard to verify the existence of NaCl in the aqueous inclusions. The crystalline ice other than amorphous ice (glasses) formed from the aqueous phase whthin the synthetic inclusions during the initial freezing, but hydrohalite did not form. Subsequent warming of these inclusions induced a phase change, typically between ap- proximately –40 and –22℃, that represents the hy- drohalite crystallization event but not a eutectic melting event. So, for fluid inclusions in the system NaCl-H2O, interpretation of phase behavior below the eutectic temperature (–20.8℃) should be made with caution. The ratios of the relative intensity and the area of Raman spectra between 3423 cm–1 peak of hydrohalite and 3098 cm–1 peak of ice show positivecorrelations to the salinities in aqueous inclusions, which can be used to determine the salinity of NaCl- H2O system inclusions.
