1 Introduction Nowadays, green chemistry has received increased attention. The use of water and scCO2 as a solvent or reagent is an important field for organic reactions and green chemistry both in laboratory and indu...1 Introduction Nowadays, green chemistry has received increased attention. The use of water and scCO2 as a solvent or reagent is an important field for organic reactions and green chemistry both in laboratory and industry.展开更多
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
On the basis of Parry’s method (1986), an improved method was established to determine the molar volume (Vm) and compositions (X) of the NaCl-H2O-CO2 (NHC) system inclusion. To use this method, the determination of V...On the basis of Parry’s method (1986), an improved method was established to determine the molar volume (Vm) and compositions (X) of the NaCl-H2O-CO2 (NHC) system inclusion. To use this method, the determination of Vm-X only requires three microthermometric data of a NHC inclusion: partial homog-enization temperature (Th ,CO2), salinity (S) and total homogenization temperature (Th). Theoretically, four associated equations are needed containing four unknown parameters: X CO2, XNaCl, Vm and F (volume fraction of CO2 phase in total inclusion when occurring partial homogenization). When they are released, the Vm-X are determined. The former three equations, only correlated with Th ,CO2, S and F, have simplified expressions:XCO2=f1(Th,CO2,S,F),XNaCl=f2(Th,CO2,S,F),Vm=f3(Th,CO2,S,F). The last one is the thermodynamic relationship of X CO2, XNaCl, Vm and Th:f4(XCO2,XNaCl,Vm,Th)=0.Since the above four associated equations are complicated, it is necessary to adopt iterative technique to release them. The technique can be described by:(i) Freely input a F value (0≤F≤1),with Th ,CO2 and S, into the former three equations. As a result,X CO 2,XNaCl and the molar volume value recorded as Vm1 are derived. (ii) Input the X CO2 and XNaCl gotten in the step above into the last equation, and another molar volume value recorded as Vm2 is determined. (iii) If Vm1 is unequal to Vm2, the calculation will be restarted from “(i)”. The iteration is completed until Vm1 is equal to Vm2, which means that the four associated equations are released. Compared to Parry’s (1986) solution method, the improved method is more convenient to use, as well as more accurate to determine X CO 2. It is available for a NHC inlusion whose partial homogenization temperature is higher than clatherate melting temperature and there are no solid salt crystals in the inclusion at parital homogenization.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the National Natural Science Foundation of China(Nos.20332030,20572027,20625205 and 20772034)Natural Science Foundation of Guangdong Province,China(No.07118070).
文摘1 Introduction Nowadays, green chemistry has received increased attention. The use of water and scCO2 as a solvent or reagent is an important field for organic reactions and green chemistry both in laboratory and industry.
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.
基金the State Key Development Program for Basic Research of China (Grant No. 2004CB720503)
文摘On the basis of Parry’s method (1986), an improved method was established to determine the molar volume (Vm) and compositions (X) of the NaCl-H2O-CO2 (NHC) system inclusion. To use this method, the determination of Vm-X only requires three microthermometric data of a NHC inclusion: partial homog-enization temperature (Th ,CO2), salinity (S) and total homogenization temperature (Th). Theoretically, four associated equations are needed containing four unknown parameters: X CO2, XNaCl, Vm and F (volume fraction of CO2 phase in total inclusion when occurring partial homogenization). When they are released, the Vm-X are determined. The former three equations, only correlated with Th ,CO2, S and F, have simplified expressions:XCO2=f1(Th,CO2,S,F),XNaCl=f2(Th,CO2,S,F),Vm=f3(Th,CO2,S,F). The last one is the thermodynamic relationship of X CO2, XNaCl, Vm and Th:f4(XCO2,XNaCl,Vm,Th)=0.Since the above four associated equations are complicated, it is necessary to adopt iterative technique to release them. The technique can be described by:(i) Freely input a F value (0≤F≤1),with Th ,CO2 and S, into the former three equations. As a result,X CO 2,XNaCl and the molar volume value recorded as Vm1 are derived. (ii) Input the X CO2 and XNaCl gotten in the step above into the last equation, and another molar volume value recorded as Vm2 is determined. (iii) If Vm1 is unequal to Vm2, the calculation will be restarted from “(i)”. The iteration is completed until Vm1 is equal to Vm2, which means that the four associated equations are released. Compared to Parry’s (1986) solution method, the improved method is more convenient to use, as well as more accurate to determine X CO 2. It is available for a NHC inlusion whose partial homogenization temperature is higher than clatherate melting temperature and there are no solid salt crystals in the inclusion at parital homogenization.
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.
