Diamond precipitation from ascending reduced fluids in the Kaapvaal lithosphere: Thermodynamic constraints

Previous research has shown that the Kaapvaal lithospheric mantle is generally reduced and characterised by a decreasing redox state with increasing depth. As a consequence, C-O-H fluids in the Kaapvaal lithospheric mantle are dominated by H₂O, CH₄, and C₂H₆. Thermodynamic calculations demonstrate that diamond precipitation from such a fluid during ascend is possible as it is exposed to a more oxidised environment and both CH₄ and C₂H₆ are oxidised. However, the calculations also demonstrate that the diamond precipitation potential from such a fluid decreases when: (1) the mantle is either more reduced or oxidised compared to the Kaapvaal mantle, or (2) the change in temperature with pressure is smaller compared to that of the Kaapvaal mantle. Therefore, the presence of reduced mantle fluid species and a generally decreasing oxygen fugacity with increasing depth do not necessarily warrant diamond precipitation from a rising reduced fluid.     

Factors Controlling Precipitation of Barite and Witherite and Genesis of the Ankang–Xunyang Barium Deposits, Shaanxi, China

The barium deposits in Ankang and Xunyang counties,Shaanxi Province,China,occur in the northernmost part of the world-class barium metallogenic belt in south Qinling.The deposits are hosted by the Lower Silurian carbonaceous siliceous rocks,with a unique combination of barite and witherite.The homogenization temperatures of fluid inclusions in the barite are mainly concentrated between 135 and 155 ℃,whereas those from the witherite have two peaks of 165-175 ℃,and 215-225℃,respectively.Laser Raman analysis of fluid inclusions indicates that the vapor phase of fluid inclusions in barite is dominated by H_2O,although some contains N_2,H_2S,and CH_4.The compositions of the vapor and liquid phases of fluid inclusions in witherite can be divided into two end-members,one dominated by H_2O without other volatiles,and the other containing CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6 in addition to H_2O.CO_2,H_2S,and some CH_4 are interpreted as products of chemical reactions during mineralization.Organic gases(CH_4,C_2H_6,C_3H_8,C_2H_4,and C_6H_6) in the fluids were critical in the formation of barium sulfate versus carbonate.The δ~(34)S values of barite range from 38.26‰ to54.23‰(CDT),the δ~(34)S values of sulfides coexisting with barium minerals vary from 22.44‰ to25.11‰(CDT),and those in the wall rock from 11.60‰ to 19.06‰(CDT).We propose that the SO_4~(2-)generally experienced bacterial sulfate reduction in seawater before mineralization,and some SO_4~(2-)also experienced thermochemical sulfate reduction in hydrothermal system during mineralization.The δ~(13)C values of witherite range from-27.30‰ to-11.80‰(PDB),suggesting that carbon was sourced from organic substances(like CH_4,C_2H_4,and C_2H_6).The formation of witherite was possibly associated with thermochemical sulfate reduction,which caused the consumption of the organic gases and SO_4~(2-) in the hydrothermal solutions,consequently inhibiting barite formation.The important conditions for forming witherite include high fluid temperatures,high Ba~(2+) concentrations,CO_2 in the fluids,low HS~- concentrations,and the subsequent rapid diffusion of H_2S during thermochemical sulfate reduction of the fluids.     

Identification and implications of fight hydrocarbon fluid inclusions from the Proterozoic Bidjovagge gold-copper deposit, Finnmark, Norway

Carbonic fluid inclusions were observed in quartz-bearing veins at the Proterozoic Bidjovagge AuCu deposit within the Kautokeino greenstone belt in Norway, where mineralization occurred in oxidation zones of graphitic schists. A primary fluid inclusion zonation was observed with C0₂-rich fluid inclusions in the structural footwall of the deposit, and CH₄-rich inclusions within the ore zone in the oxidation zone. Microthermometry of the primary hydrocarbon inclusions revealed 2 groups; (1) a group which homogenized between −125°C and the critical temperature of CH₄ (−82.1°C), which indicated the presence of pure CH₄, and (2) a group which homogenized between the critical temperature of CH₄ and −42°C, which indicated the presence CH₄ and higher hydrocarbons (HHC). Raman microprobe analyses of the first group confirmed the presence of CH₄. The second inclusion group were fluorescent, and Raman spectra clearly displayed CH₄,C₂H₆, and rarer C₃H₈ peaks. A typical feature of the Raman spectra were elevated baselines at the hydrocarbon peaks. Carbon peaks were also usually detected in each inclusion by Raman analysis. Bulk gas chromatography analyses of samples containing the first group (CH₄) indicated the presence of CH₄ and low concentrations of C₂H₆ and C₃H₈. Gas chromatography analyses of samples containing the second group (CH₄ and higher hydrocarbons) confirmed the presence of CH₄, and higher hydrocarbons such as C₂H₆ and C₃H₈ and also butanes. Based on the spacial zonation of hydrocarbons and the estimated PT conditions of 300 to 375°C and 2 to 4 kbars, the authors suggest an abiotic origin for the hydrocarbons. It is suggested that the hydrothermal fluids oxidized the graphitic schist, precipitated Cu and Au and formed light gas hydrocarbons.     

Detailed compositional analysis of gas seepage at the National Carbon Storage Test Site,Teapot Dome,Wyoming, USA

A baseline determination of CO₂ and CH₄ fluxes and soil gas concentrations of CO₂ and CH₄ was made over the Teapot Dome oil field in the Naval Petroleum Reserve No. 3 (NPR-3) in Wyoming, USA. This was done in anticipation of experimentation with CO₂ sequestration in the Pennsylvanian Tensleep Sandstone underlying the field at a depth of 1680 m.The baseline data were collected during the winter, 2004 in order to minimize near-surface biological activity in the soil profile. The baseline data were used to select anomalous locations that may be the result of seeping thermogenic gas, along with background locations. Five 10-m holes were drilled, 3 of which had anomalous gas microseepage, and 2 were characterized as “background.” These were equipped for nested gas sampling at depths of 10-, 5-, 3-, 2-, and 1-m depths. Methane concentrations as high as 170,000 ppmv (17%) were found, along with high concentrations of C₂H₆, C₃H₈, n-C₄H₁₀, and i-C₄H₁₀. Much smaller concentrations of C₂H₄ and C₃H₆ were observed indicating the beginning of hydrocarbon oxidation in the anomalous holes. The anomalous 10-m holes also had high concentrations of isotopically enriched CO₂, indicating the oxidation of hydrocarbons. Concentrations of the gases decreased upward, as expected, indicating oxidation and transport into the atmosphere. The ancient source of the gases was confirmed by ¹⁴C determinations on CO₂, with radiocarbon ages approaching 38 ka within 5 m of the surface.Modeling was used to analyze the distribution of hydrocarbons in the anomalous and background 10-m holes. Diffusion alone was not sufficient to account for the hydrocarbon concentration distributions, however the data could be fit with the addition of a consumptive reaction. First-order rate constants for methanotrophic oxidation were obtained by inverse modeling. High rates of oxidation were found, particularly near the surface in the anomalous 10-m holes, demonstrating the effectiveness of the process in the attenuation of CH₄ microseepage. The results also demonstrate the importance of CH₄ measurements in the planning of a monitoring and verification program for geological CO₂ sequestration in sites with significant remaining hydrocarbons (i.e. spent oil reservoirs).     

Composition and origin of coalbed gases in the Lower Silesian basin,southwest Poland

Coalbed gases in the Lower Silesian Coal Basin (LSCB) of Poland are highly variable in both their molecular and stable isotope compositions. Geochemical indices and stable isotope ratios vary within the following ranges: hydrocarbon (C_HC) index C_HC=CH₄/(C₂H₆₊ C₃H₈) from 1.1 to 5825, wet gas (C₂₊) index C₂₊=(C₂H₆₊ C₃H₈₊ C₄H₁₀₊ C₅H₁₂) / (CH₄₊ C₂H₆₊ C₃H₈₊ C₄H₁₀₊ C₅H₁₂) 100 (%) from 0.0 to 48.3%, CO₂–CH₄ (CDMI) index CDMI=CO₂/(CO₂₊ CH₄) 100 (%) from 0.1 to 99.9%, δ¹³C(CH₄) from −66.1 to −24.6‰, δD(CH₄) from −266 to −117‰, δ¹³C(C₂H₆) from −27.8 to −22.8‰, and δ¹³C(CO₂) from −26.6 to 16.8‰. Isotopic studies reveal the presence of 3 genetic types of natural gases: thermogenic (CH₄, higher gaseous hydrocarbons, and CO₂), endogenic CO₂, and microbial CH₄ and CO₂. Thermogenic gases resulted from coalification processes, which were probably completed by Late Carboniferous and Early Permian time. Endogenic CO₂ migrated along the deep-seated faults from upper mantle and/or magma chambers. Minor volumes of microbial CH₄ and CO₂ occur at shallow depths close to the abandoned mine workings. “Late-stage” microbial processes have commenced in the Upper Cretaceous and are probably active at present. However, depth-related isotopic fractionation which has resulted from physical and physicochemical (e.g. diffusion and adsorption/desorption) processes during gas migration cannot be neglected. The strongest rock and gas outbursts occur only in those parts of coal deposits of the LSCB which are dominated by large amounts of endogenic CO₂.     

Light hydrocarbons geochemistry of surface sediments from Pranhita-Godavari Basin,Andhra Pradesh

A geochemical study of surface sediments from Pranhita-Godavari Basin, Andhra Pradesh, India was carried out using light hydrocarbon compounds to assess the hydrocarbon potential of the basin. Suite of 80 soil samples were collected from the depth of 2.5 m and analyzed for adsorbed light gaseous hydrocarbons namely methane (CH₄), ethane (C₂H₆) and propane (C₃H₈) in Gas chromatograph. Compound specific Carbon isotope ratios for CH₄ and C₂H₆ were also determined using GC-C IRMS (Gas Chromatograph Combustion Isotope Mass Spectrometer). The presence of moderate to low concentrations of methane (C_CH4 C_{CH_4 } : 1 to 138 ppb), ethane (H₄{H_4 }: 1 to 35 ppb) and propane (C_{C3 H8} C_{C_3 H_8 } : 1 to 20 ppb) was measured in the soil samples. Carbon isotopic composition of d¹³ C_CH4 \delta ^{13} C_{CH_4 } ranges between −27.9 to −47.1 ‰ and d¹³ C_{C2 H6} \delta ^{13} C_{C_2 H_6 } ranged between −36.9 to −37.2 ‰ (V-PDB) indicating that these gases are of thermogenic origin. Study of soil samples suggests the area has good potential for hydrocarbon.     

Prediction of CH4 and CO2 hydrate phase equilibrium and cage occupancy from ab initio intermolecular potentials

Presented is an improved model for the prediction of phase equilibria and cage occupancy of CH₄ and CO₂ hydrate in aqueous systems. Different from most hydrate models that employ Kihara potential or Lennard-Jones potential with parameters derived from experimental phase equilibrium data of hydrates, we use atomic site-site potentials to account for the angle-dependent molecular interactions with parameters directly from ab initio calculation results. Because of this treatment, our model can predict the phase equilibria of CH₄ hydrate and CO₂ hydrate in binary systems over a wide temperature-pressure range (from 243-318 K, and from 10-3000 bar for CH₄ hydrate; from 253-293 K, and from 5-2000 bar for CO₂ hydrate) with accuracy close to experiment. The average deviation of this model from experimental data is less than 3% in pressures for a given temperature. This accuracy is similar to previous models for pressures below 500 bar, but is more accurate than previous models at higher pressures. This model is also capable of predicting the cage occupancy and hydration number for CH₄ hydrate and CO₂ hydrate without fitting any experimental data. The success of this study validates the predictability of ab initio intermolecular potentials for thermodynamic properties.     

Abiotic formation of hydrocarbons under hydrothermal conditions: Constraints from chemical and isotope data

To understand reaction pathways and isotope systematics during mineral-catalyzed abiotic synthesis of hydrocarbons under hydrothermal conditions, experiments involving magnetite and CO₂ and H₂-bearing aqueous fluids were conducted at 400 °C and 500 bars. A robust technique for sample storage and transfer from experimental apparatus to stable isotope mass spectrometer provides a methodology for integration of both carbon and hydrogen isotope characterization of reactants and products generated during abiogenic synthesis experiments. Experiments were performed with and without pretreatment of magnetite to remove background carbon associated with the mineral catalyst. Prior to experiments, the abundance and carbon isotope composition of all carbon-bearing components were determined. Time-series samples of the fluid from all experiments indicated significant concentrations of dissolved CO and C₁-C₃ hydrocarbons and relatively large changes in dissolved CO₂ and H₂ concentrations, consistent with formation of additional hydrocarbon components beyond C₃. The existence of relatively high dissolved alkanes in the experiment involving non-pretreated magnetite in particular, suggests a complex catalytic process, likely involving reinforcing effects of mineral-derived carbon with newly synthesized hydrocarbons at the magnetite surface. Similar reactions may be important mechanisms for carbon reduction in chemically complex natural hydrothermal systems. In spite of evidence supporting abiotic hydrocarbon formation in all experiments, an “isotopic reversal” trend was not observed for ¹³C values of dissolved alkanes with increasing carbon number. This may relate to the specific mechanism of carbon reduction and hydrocarbon chain growth under hydrothermal conditions at elevated temperatures and pressures. Over time, significant ¹³C depletion in CH₄ suggests either depolymerization reactions occurring in addition to synthesis, or reactions between the C₁-C₃ hydrocarbons and carbon species absorbed on mineral surfaces and in solution.     

Phase relations in the CH4-H2O-NaCl system at 2 kbar, 300 to 600°C as determined using synthetic fluid inclusions

Synthesis of fluid inclusions in the CH₄-H₂O-NaCl system was accomplished by subjecting fractured quartz or fluorite, along with known quantities of CH₄, H₂O, and NaCl, to a pressure of 2 kbar and temperatures of 300, 400, 500, or 600°C, in sealed Au capsules. Under the elevated P-T conditions, some of the fractures healed, trapping fluids as inclusions. Microthermometric measurements conducted on the fluid inclusions show that at 2 kbar and 400 to 600°C, there are very broad regions of fluid unmixing in the CH₄-H₂O-NaCl system. For those bulk fluid compositions that lie in the two-phase (i.e., immiscible fluids) field, the high-density phase is enriched in NaCl, whereas the low-density phase is enriched in CH₄. For any given bulk composition, the degree of NaCl enrichment in the high-density phase increases, whereas the degree of CH₄ enrichment in the low-density phase decreases, as temperature increases from 400 to 600°C. Our experimental constraints on the size of the two-phase field are generally consistent with results generated using the equation-of-state GEOFLUIDS (available at http://geotherm.ucsd.edu/geofluids/). However, when comparing the compositions of coexisting immiscible fluids, as determined experimentally vs. calculated using GEOFLUIDS, we find that some relatively small but probably significant differences exist between our experiments and this equation of state.     

Fluid regime and diamond formation in the reduced mantle: Experimental constraints

The composition and potential diamond productivity of C–O–H fluids that could exist in the reduced regions of the Earth’s upper mantle and in the mantles of Uranus and Neptune were studied in experiments at 6.3 GPa and 1400–1600 °C and durations of 15–48 h. Hydrogen fugacity in the fluid phase was controlled by the Mo–MoO₂ or Fe–FeO buffers, using a specially modified double-capsule method. The oxygen fugacity in the samples was controlled by adding different amounts of water, stearic acid, anthracene, and docosane to a graphite charge. At high P–T conditions, the degree of decomposition of the heavy hydrocarbons added to the charge was 99.9%. The composition of the fluids coexisting with graphite/diamond in the buffered experiments varied from H₂O  H₂ > CH₄ (at fO₂ somewhat lower than the “water maximum”) to H₂ > CH₄ > (C₂H₄ + C₂H₆)>C₃H₈ (in C–H system). In the C–H system the maximum concentrations of major species in the synthesized fluid were: H₂ = 79 mol.% and CH₄ = 21 mol.%. The composition of the H₂-rich fluids, which were synthesized at 6.3 GPa and 1400–1600 °C for the first time, differs considerably from that of the ultra-reduced CH₄-rich fluids stable at 2.0–3.5 GPa and 1000–1300 °C. Thermodynamic calculations of the reduced C–O–H fluids at the P–T conditions of the experiments revealed CH₄-rich compositions (CH₄  H₂ > (C₂H₄ + C₂H₆)>C₃H₈), which however drastically differed from the synthesized compositions. The rates of diamond nucleation and growth in the experiments depended on the fluid composition. Diamond crystallization had a maximum intensity in the pure aqueous fluids, while in the H₂-rich fluids no diamond formation was observed. Only metastable graphite precipitated from the ultra-reduced fluids. The type of the initial hydrocarbon used for the fluid generation did not affect this process.     

Carbon and hydrogen isotopic evidence for the origin of combustible gases in water-supply wells in north-central Pennsylvania

The origin of the combustible gases in groundwater from glacial-outwash and fractured-bedrock aquifers was investigated in northern Tioga County, Pennsylvania. Thermogenic methane (CH₄) and ethane (C₂H₆) and microbial CH₄ were found. Microbial CH₄ is from natural in situ processes in the shale bedrock and occurs chiefly in the bedrock aquifer. The δ¹³C values of CH₄ and C₂H₆ for the majority of thermogenic gases from water wells either matched or were between values for the samples of non-native storage-field gas from injection wells and the samples of gas from storage-field observation wells. Traces of C₂H₆ with microbial CH₄ and a range of C and H isotopic compositions of CH₄ indicate gases of different origins are mixing in sub-surface pathways; gas mixtures are present in groundwater. Pathways for gas migration and a specific source of the gases were not identified. Processes responsible for the presence of microbial gases in groundwater could be elucidated with further geochemical study.     

Carbon and hydrogen isotopic evidence for the origin of combustible gases in water-supply wells in north-central Pennsylvania

The origin of the combustible gases in groundwater from glacial-outwash and fractured-bedrock aquifers was investigated in northern Tioga County, Pennsylvania. Thermogenic methane (CH₄) and ethane (C₂H₆) and microbial CH₄ were found. Microbial CH₄ is from natural in situ processes in the shale bedrock and occurs chiefly in the bedrock aquifer. The δ¹³C values of CH₄ and C₂H₆ for the majority of thermogenic gases from water wells either matched or were between values for the samples of non-native storage-field gas from injection wells and the samples of gas from storage-field observation wells. Traces of C₂H₆ with microbial CH₄ and a range of C and H isotopic compositions of CH₄ indicate gases of different origins are mixing in sub-surface pathways; gas mixtures are present in groundwater. Pathways for gas migration and a specific source of the gases were not identified. Processes responsible for the presence of microbial gases in groundwater could be elucidated with further geochemical study.     

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/.     

Stability of methane in reduced C–O–H fluid at 6.3 GPa and 1300–1400°C

The composition of a reduced C–O–H fluid was studied by the method of chromatography–mass spectrometry under the conditions of 6.3 GPa, 1300–1400°C, and fO₂ typical of the base of the subcratonic lithosphere. Fluids containing water (4.4–96.3 rel. %), methane (37.6–0.06 rel. %), and variable concentrations of ethane, propane, and butane were obtained in experiments. With increasing fO₂, the proportion of the CH₄/C₂H₆ peak areas on chromatograms first increases and then decreases, whereas the CH₄/C₃H₈ and CH₄/C₄H₁₀ ratios continually decrease. The new data show that ethane and heavier HCs may be more stable to oxidation, than previously thought. Therefore, when reduced fluids pass the “redox-front,” carbon is not completely released from the fluid and may be involved in diamond formation.     

The separate production of H2S from the thermal reaction of hydrocarbons with magnesium sulfate and sulfur: Implications for thermal sulfate reduction

The yields and stable C and H isotopic composition of gaseous products from the reactions of pure n-C₂₄ with (1) MgSO₄; and (2) elemental S in sealed Au-tubes at a series of temperatures over the range 220–600 °C were monitored to better resolve the reaction mechanisms. Hydrogen sulfide formation from thermochemical sulfate reduction (TSR) of n-C₂₄ with MgSO₄ was initiated at 431 °C, coincident with the evolution of C₂–C₅ hydrocarbons. Whereas the yields of H₂S increased progressively with pyrolysis temperature, the hydrocarbon yields decreased sharply above 490 °C due to subsequent S consumption. Ethane and propane were initially very ¹³C depleted, but became progressively heavier with pyrolysis temperature and were more ¹³C enriched than the values of a control treatment conducted on just n-C₂₄ above 475 °C. TSR of MgSO₄ also led to progressively higher concentrations of CO₂ showing relatively low δ¹³C values, possibly due to input of isotopically light CO₂ derived from gaseous hydrocarbon oxidation (e.g., more depleted CH₄).     

长江中下游成矿带矽卡岩型矿床矿物包裹体激光拉曼分析结果及其地质-地球化学意义

矽卡岩矿床各种硅酸盐矿物中熔融包裹体和流体-熔融包裹体的显微测温资料和相成分让我们提出过大量矽卡岩是岩浆成因的建议。在本文中,我们提供沿长江中下游成矿带的许多矽卡岩矿床包含在石榴子石和辉石里的熔融包裹体和流体-熔融包裹体的激光拉曼分析结果,目的是证明所研究的并与Cu-Fe-Au矿床共生的矽卡岩系岩浆成因。我们的研究结果显示,熔融包裹体只含固体相和微量气相。流体-熔融包裹体除了含大量固相外,还含微量流体和气相以及没有被仪器检测到的气体。固体相与包裹体寄主矿物相同或类似。流体相主要为水或盐水溶液和包括C6H6、C3H6、C3H8、CH4、CO2和O2的气体。我们提出,熔融包裹体和流体-熔融包裹体是原始岩浆的最好代表。这就证明,矽卡岩组合是由一个原生岩浆直接结晶而成。此外,我们还讨论了岩浆矽卡岩形成的温度、分布范围和规模、形成机制和与Cu-Fe-Au矿化作用的联系。     

On saturation of magnesian cordierite with alkanes at high temperatures and pressures

 Incorporation of hydrocarbons (CH₄, C₂H₆, C₃H₈, C₄H₁₀) in cordierite channels was experimentally studied at 700 °C and at pressures from 200 to 1000 MPa, (avoiding recrystallization). The maximum concentrations of hydrocarbons determined by gas chromatographic analysis are CH₄=78.3, C₂H₆=134, C₂H₄ + C₂H₆=26, C₃H₈=28, C₄H₁₀=32, C₅H₁₂=23, and C₆H₁₄=7 × 10⁻³ wt%). According to IR spectroscopy data, the channel forms of hydrocarbons differ from the forms on the surface. As a result of interactions with the framework oxygen, normal hydrocarbons are converted to saturated oligomers and their fragments. Small amounts of water molecules of the first and second types (up to 0.3 wt%) are formed in the same way. As pressure grows from 200 to 1000 MPa, the total content of structural hydrocarbons is nearly doubled. Special runs on cordierite saturation in mixtures of hydrocarbons with water showed that low contents of hydrocarbons in natural cordierites correspond to their large concentrations in fluid. Received: 7 May 2001 / Accepted: 17 July 2001     

车载小型气体质谱仪现场地气分析应用

OmniStar小型气体质谱仪用于车载实验室,可根据野外情况采取灵活的采样方式,实现对H2、He、CH4、N2、O2、Ar、CO2以及C3H8、C4H10的现场分析。对浓度为100×10-6的H2、He、CH4、N2、O2、Ar、CO2混合标气进行100次连续测定,得到的各组分的精密度(RSD)均优于1%,H2、He、Ar、CO2准确度(RE)分别为3.74、0.94、1.83、10.5;对室内空气进行连续3 500次测定,得到的H2、He、CO2的精密度分别为2.25%、5.55%、4.06%,N2、O2、Ar的精密度优于1%;对CH4、C2H6、C3H8、C4H10混合标准气体进行连续13次测量,得到的C3H8、C4H10的精密度(RSD)优于1%,测量的平均值与标准值完全吻合,能够满足野外现场分析需求。在内蒙古西乌旗及新疆金窝子地区应用该仪器,采用采样袋取气、螺旋钻及井孔原位在线测定等方式得到样品数据,并发现两区域内部分采样点的CO2、H2及He异常。     

Experimental Study of the SiO<Subscript>2</Subscript>–H<Subscript>2</Subscript>O–KF–KCl–NaF System at 700–800°C and 1–2 kbar Based on Synthetic Fluid Inclusions in Quartz

The phase state of the fluid in the H₂O–KF ± KCl ± NaF system is studied in the presence of quartz for an experimental assay of the mutual influence of various salts of the fluid-forming mixture on heterogeneous fluid equilibria. The fluid inclusions were synthesized in quartz by the fracture healing method from solutions with KF + KCl and KF + NaF mixtures at 1 or 2 kbar and 700, 750, or 800°C. The results of the fluid inclusion study indicate a heterogeneous state of the fluid and variation in the fluid composition during experiments as a result of its interaction with quartz. The increase in temperature and pressure, as well as variation in the proportions of the salt contents in the fluid-forming mixture, changed the course of chemical reactions. After all the experiments, a glassy phase was observed in some types of inclusions. It is known that aqueous KF or KCl solutions, the solubility of which increases during heating, are characterized by phase equilibria of systems of the first type (Valyashko, 1990), when liquid and vapor are equilibrated for a heterogeneous state of the fluid. In this case, some inclusions should homogenize to vapor. However, no similar inclusions were observed in contrast to denser fluid phases (liquids), which are typical of the upper heterogeneous area of systems of the second (P–Q) type. Some inclusions host solid phases, the solubility of which decreases as the temperature increases. The results of experiments in the presence of KF + NaF solutions showed that the amount of inclusions of heterogeneous entrapment increases at higher temperatures simultaneously with a decrease in the H₂O content of the glassy phase.     

Carbon and hydrogen isotopic compositions of New Zealand geothermal gases

Carbon and hydrogen isotopic compositions are reported for methane, hydrogen and carbon dioxide from four New Zealand geothermal areas: Ngawha, Wairakei, Broadlands and Tikitere. Carbon-13 contents are between ?24.4 and ?29.5%. (PDB) for methane, and between ?3.2 and ?9.1%. for carbon dioxide. Deuterium contents are between ?142 and ?197%. (SMOW) for methane and between ?310 and ?600%. for hydrogen. The different areas have different isotopic compositions with some general relationships to reservoir temperature.The isotopic exchange of hydrogen with water indicates acceptable reservoir temperatures of 180–260°C from most spring samples but often higher than measured temperatures in well samples. Indicated temperatures assuming ¹³C equilibria between CH₄ and CO₂ are 100–200°C higher than measured maxima. This difference may be due to partial isotopic equilibration or may reflect the origin of the methane. Present evidence cannot identify whether the methane is primordial, or from decomposing sediments or from reduction of magmatic CO₂. The isotopic equilibria between CH₄, CO₂, H₂ and H₂O are reviewed and a new semi-empirical temperature scale proposed for deuterium exchange between methane and water.