Stable carbon isotope composition and concentrations of CO₂ and CH₄ in the deep catotelm of a peat bog     

Philipp Steinmann  Bernd Eilrich  Markus Leuenberger 《Geochimica et cosmochimica acta》2008,72(24):6015-6026

Vertical profiles of concentration and C-isotopic composition of dissolved methane and carbon dioxide were observed over 26 months in the catotelm of a deep (6.5 m) peat bog in Switzerland. The dissolved concentrations of these gases increase with depth while CO₂ predominates over CH₄ (CO₂ ca. 5 times CH₄). This pattern can be reproduced by a reaction-advection-ebullition model, where CO₂ and CH₄ are formed in a ratio of 1:1. The less soluble methane is preferentially lost via outgassing (bubbles). The isotopic fractionation between CO₂ and CH₄ also increases with depth, with α_C values ranging from 1.045 to 1.075. The isotopic composition of the gases traces the passage of respiration-derived CO₂ (from the near surface) through a shallow zone with methanogenesis of low isotopic fractionation (splitting of fermentation-derived acetate). This solution then moves through the catotelm, where methanogenesis occurs by CO₂ reduction (large isotopic fractionation). In the upper part of the catotelm the C-13-depleted respiration-derived CO₂ pool buffers the isotopic composition of CO₂; the δ¹³C of CO₂ increases only slowly. At the same time strongly depleted CH₄ is formed as CO₂ reduction consumes the depleted CO₂. In the lower part of the catotelm, the respiration-derived CO₂ and shallow CH₄ become less important and CO₂ reduction is the dominant source of CO₂ and CH₄. Now, the δ¹³C values of both gases increase until equilibrium is reached with respect to the isotopic composition of the substrate. Thus, the δ¹³C values of methane reach a minimum at intermediate depth, and the deep methane has δ¹³C values comparable to shallow methane. A simple mixing model for the isotopic evolution is suggested. Only minor changes of the observed patterns of methanogenesis (in terms of concentration and isotopic composition) occur over the seasons. The most pronounced of these is a slightly higher rate of acetate splitting in spring.  相似文献   

Methane-producing bacteria: natural fractionations of the stable carbon isotopes   总被引：1，自引：0，他引：1  

Larry M. Games  J.M. HayesRobert  P. Gunsalus 《Geochimica et cosmochimica acta》1978,42(8):1295-1297

The ${}^{13}\text{C}{}^{12}\text{C}$ fractionation factors ($\text{CO}{}_2\text{CH}{}_4$) for the reduction of CO₂ to CH₄ by pure cultures of methane-producing bacteria are, for Methanosarcina barkeri at 40°C, 1.045 ± 0.002; for Methanobacterium strain M.o.H. at 40°C, 1.061 ± 0.002; and, for Methanobacterium thermoautotrophicum at 65°C, 1.025 ± 0.002. These observations suggest that the acetic acid used by acetate dissimilating bacteria, if they play an important role in natural methane production, must have an intramolecular isotopic fractionation ($\text{CO}{}_2\text{H}\text{CH}{}_3$) approximating the observed $\text{CO}{}_2\text{CH}{}_4$ fractionation.  相似文献   

Geochemical and isotopic characteristics of fluids in the Niutuozhen geothermal field,North China     

Jumei Pang  Zhonghe Pang  Min Lv  Jiao Tian  Yanlong Kong 《Environmental Earth Sciences》2018,77(1):12

Niutuozhen geothermal field is located in the Jizhong graben, belonging to the northern part of Bohai Bay Basin in North China. Chemical and isotopic analyses were carried out on 14 samples of the geothermal fluids discharged from Neogene Minghuazhen (Nm), Guantao (Ng), and Jixianian Wumishan (Jxw) formations. The δ²H and δ¹⁸O in water, δ¹³C in CH₄, δ¹³C in CO₂, and ³He/⁴He ratio in the gases were analyzed in combination with chemical analyses on the fluids in the Niutuozhen geothermal field. The chemical and isotopic compositions indicate a meteoric origin of the thermal waters. The reservoir temperatures estimated by chemical geothermometry are in the range between 60 and 108 °C. The results show that the gases are made up mainly by N₂ (18.20–97.42 vol%), CH₄ (0.02–60.95 vol%), and CO₂ (0.17–25.14 vol%), with relatively high He composition (up to 0.52 vol%). The chemical and isotopic compositions of the gas samples suggest the meteoric origin of N₂, predominant crustal origins of CH₄, CO₂, and He. The mantle-derived He contributions are calculated to be from 5 to 8% based on a crust–mantle binary mixing model. The deep temperatures in the Jxw reservoir were evaluated based on gas isotope geothermometry to be in the range from 141 to 165 °C. The mantle-derived heat fraction in the surface heat flow is estimated to be in the range of 48–51% based on ³He/⁴He ratios.  相似文献   

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

N Guilhaumou  P Dhamelincourt  J-C Touray  J Touret 《Geochimica et cosmochimica acta》1981,45(5):657-673

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

Carbon and hydrogen isotopic compositions of New Zealand geothermal gases   总被引：1，自引：0，他引：1  

G.L Lyon  J.R Hulston 《Geochimica et cosmochimica acta》1984,48(6):1161-1171

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.  相似文献   

T-X_CO2 stability relations and phase equilibria of a calcic carbonate scapolite     

Bruce G. Aitken 《Geochimica et cosmochimica acta》1983,47(3):351-362

At a total pressure of 5 kb, calcic, Cl-free scapolite (Me₈₃) is stable relative to plagioclase-bearing assemblages at $\text{T ≧ 625°C}$, . With decreasing temperature, scapolite breaks down to plagioclase + calcite. Scapolite is replaced by plagioclase + grossular + cancrinite + CO₂ in the presence of H₂O-rich fluids. The stable coexistence of scapolite and calcite, an assemblage typical of most natural occurrences of calcic scapolite, is limited by the reaction: scapolite + calcite → grossular + cancrinite + CO₂, which occurs at 750°C, X_CO2 = 0.46; 700°C, X_CO2 = 0.33; 650°C, X_CO2 = 0.18, for the chosen bulk composition.Generalization of the experimental results to encompass the complete range of fully carbonated scapolite compositions indicates that mizzonite (Me₇₅) has the largest T-X_CO2 stability field. For scapolite more calcic than mizzonite, stable growth is restricted to conditions of increasingly higher temperature and X_CO2.The experimental results are consistent with various petrologic features of scapolite-bearing rocks, particularly scapolite-clinopyroxene granulites, and indicate that such rocks were formed in the presence of CO₂-rich fluids.  相似文献   

Stable carbon isotopes of HCO₃⁻ in oil-field waters—implications for the origin of CO₂     

William W. Carothers  Yousif K. Kharaka 《Geochimica et cosmochimica acta》1980,44(2):323-332

The δ¹³C values of dissolved HCO₃^? in 75 water samples from 15 oil and gas fields (San Joaquin Valley, Calif., and the Houston-Galveston and Corpus Christi areas of Texas) were determined to study the sources of CO₂ of the dissolved species and carbonate cements that modify the porosity and permeability of many petroleum reservoir rocks. The reservoir rocks are sandstones which range in age from Eocene through Miocene. The δ¹³C values of total HCO₃^? indicate that the carbon in the dissolved carbonate species and carbonate cements is mainly of organic origin.The range of δ¹³C values for the HCO₃^? of these waters is ?20–28 per mil relative to PDB. This wide range of δ¹³C values is explained by three mechanisms. Microbiological degradation of organic matter appears to be the dominant process controlling the extremely low and high δ¹³C values of HCO₃^? in the shallow production zones where the subsurface temperatures are less than 80°C. The extremely low δ¹³C values (< ?10 per mil) are obtained in waters where concentrations of SO₄^2? are more than 25 mg/l and probably result from the degradation of organic acid anions by sulfate-reducing bacteria (SO₄^2? + CH₃COO^? → 2HCO₃^? + HS^?). The high δ¹³C values probably result from the degradation of these anions by methanogenic bacteria (CH₃COO^? + H₂OaiHCO₃^? + CH₄).Thermal decarboxylation of short-chain aliphatic acid anions (principally acetate) to produce CO₂ and CH₄ is probably the major source of CO₂ for production zones with subsurface temperatures greater than 80°C. The δ¹³C values of HCO₃^? for waters from zones with temperatures greater than 100°C result from isotopic equilibration between CO₂ and CH₄. At these high temperatures, δ¹³C values of HCO₃^? decrease with increasing temperatures and decreasing concentrations of these acid anions.  相似文献   

Experimental confirmation of the lack of carbon isotope exchange between methane and carbon oxides at high temperatures     

William M. Sackett  H.Moses Chung 《Geochimica et cosmochimica acta》1979,43(2):273-276

  相似文献   

Stable hydrogen isotopes in iron oxides—isotope effects associated with the dehydration of a natural goethite     

Crayton J. Yapp 《Geochimica et cosmochimica acta》1983,47(7):1277-1287

The dehydration of a natural goethite to hematite is accompanied by a systematic hydrogen isotope fractionation. Closed system dehydration at, and below, 250°C results in a significantly greater degree of isotopic fractionation than does open system dehydration. This relationship is apparently reversed at 300°C. Both processes produce a progressive decrease in the $\text{D}\text{H}$ ratio of the mineral hydrogen with increasing degree of dehydration. At temperatures of 160°C to 250°C the closed system mineralvapor fractionation factor is independent of temperature, while above 250°C, it varies strongly with temperature. The mineral-vapor fractionation factor associated with open system dehydration appears to be independent of temperature over the interval 160°C to 300°C. The closed system $\text{D}\text{H}$ fractionation suggests that natural goethite undergoing dehydration in the presence of water can isotopically exchange with that water.CO₂ loss from goethite during dehydration is correlated with the loss of H₂O. The CO₃ is thought to be present in carbonates which exist as impurities in the goethite. Loss of both H₂O and CO₂ appears to be diffusion-controlled.  相似文献   

New gas geothermometers for geothermal exploration—calibration and application     

Stefán Arnórsson  Einar Gunnlaugsson 《Geochimica et cosmochimica acta》1985,49(6):1307-1325

Calibration of five gas geothermometers is presented, three of which used CO₂, H₂S and H₂ concentrations in fumarole steam, respectively. The remaining two use $\text{CO}{}_2\text{H}{}_2$ and $\text{H}{}_2\text{S}\text{H}{}_2$ ratios. The calibration is based on the relation between gas content of drillhole discharges and measured aquifer temperatures. After establishing the gas content in the aquifer, gas concentrations were calculated in steam formed by adiabatic boiling of this water to atmospheric pressure to obtain the gas geothermometry functions. It is shown that the concentrations of CO₂, H₂S and H₂ in geothermal reservoir waters are fixed through equilibria with mineral buffers. At temperatures above 230°C epidote + prehnite + calcite + quartz are considered to buffer CO₂. Two buffers are involved for H₂S and H₂ and two functions are, therefore, presented for the geothermometers involving these gases. For waters containing less than about 500 ppm chloride and in the range 230–300°C pyrite + pyrrholite + epidote + prehnite seem to be involved, but pyrite + epidote + prehnite + magnetite or chlorite for waters above 300°C and waters in the range 230–300°C, if containing over about 500 ppm.The gas geothermometers are useful for predicting subsurface temperatures in high-temperature geothermal systems. They are applicable to systems in basaltic to acidic rocks and in sediments with similar composition, but should be used with reservation for systems located in rocks which differ much in composition from the basaltic to acidic ones. The geothermometry results may be used to obtain information on steam condensation in upflow zones, or phase separation at elevated pressures.Measured aquifer temperatures in drillholes and gas geothermometry temperatures, based on data from nearby fumaroles, compare well in the five fields in Iceland considered specifically for the present study as well as in several fields in other countries for which data were inspected. The results of the gas geothermometers also compare well with the results of solute geothermometers and mixing models in three undrilled Icelandic fields.  相似文献   

Chemical and isotopic equilibrium between CO₂ and CH₄ in fumarolic gas discharges: Generation of CH₄ in arc magmatic-hydrothermal systems     

Jens Fiebig  Giovanni Chiodini  Andrea Rizzo  Johannes C. Hunziker 《Geochimica et cosmochimica acta》2004,68(10):2321-2334

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH₄) within two subduction-related magmatic-hydrothermal environments.Apparent temperatures derived from carbon isotope partitioning between CH₄ and CO₂ of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H₂O-H₂-CO₂-CO-CH₄ geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH₄, CO₂ and H₂O implying that carbon isotope partitioning between CO₂ and CH₄ in both systems is controlled by aquifer temperature.N₂/³He and CH₄/³He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH₄ may have been primarily generated through the reduction of CO₂ by H₂ in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH₄ and subsequent re-equilibration with co-existing CO₂ cannot be ruled out entirely. CO₂/³He ratios and δ¹³C_CO2 values imply that the evolved CO₂ either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH₄ during thermometamorphism.  相似文献   

The chemistry of geothermal waters in Iceland. III. Chemical geothermometry in geothermal investigations     

Stefán Arnórsson  Einar Gunnlaugsson  Hördur Svavarsson 《Geochimica et cosmochimica acta》1983,47(3):567-577

New data from geothermal wells in Iceland have permitted empirical calibration of the chalcedony and $\text{Na}\text{K}$ geothermometers in the range of 25–180°C and 25–250°C respectively. The temperature functions are: Concentrations are expressed in ppm. These temperature functions correspond well with the chalcedony solubility data of Fournier (1973) and the thermodynamic data for low-albite/microcline/solution equilibria of Heloeson (1969).A new CO₂ geothermometer is proposed which is considered to be useful in estimating underground temperatures in fumarolic geothermal fields. Its application involves analysis of CO₂ concentrations in the fumarole steam. The temperature function which applies in the range 180?300°C is: logCO₂ = 37.43 + 73192/T- 11829· 10₃/T² + 0.18923T- 86.187·logT where T is in °K and CO₂ in moles per kg of steam.  相似文献   

Calculation of the thermodynamic and geochemical consequences of nonideal mixing in the system H₂O-CO₂-NaCl on phase relations in geologic systems: Equation of state for H₂O-CO₂-NaCl fluids at high pressures and temperatures   总被引：1，自引：0，他引：1  

Teresa Suter Bowers  Harold C. Helgeson 《Geochimica et cosmochimica acta》1983,47(7):1247-1275

Fluid inclusion analyses leave little doubt that solutions containing large concentrations of H₂O, CO₂, and electrolytes are involved in a wide range of geologic processes. Although the miscibility gap in the system H₂O-CO₂ occurs only at low temperatures, experimental data reported by Takenouchi and Kennedy (1965) and Gehrig (1980) indicate that the addition of 6 weight percent NaCl relative to H₂O + Nacl extends the region of immiscibility in the system H₂O-CO₂-NaC] to ≥700°C at 500 bars and mole fractions of CO₂ (X_CO2) ? 0.1. In contrast, addition of 20 weight percent NaCl relative to H₂O + NaCl at 700°C and 500 bars expands the miscibility gap to X_CO2 ? 0.2. At 2000 bars, addition of 20 and 35 weight percent NaCl relative to H₂O + NaCl causes the miscibility gap to extend to ~500° and ~700°C, respectively, at . The existence of the immiscible region in this high-pressure/temperature environment has a profound effect on temperatures of equilibration for metamorphic mineral assemblages (Bowers and Helgeson, 1983). To determine the extent to which nonideality in the ternary system affects these equilibria, the modified Redlich-Kwong (MRK.) equation of state was fit to pressure-volume-temperature data taken from Gehrig (1980) along pseudobinaries for which is constant. Fugacity coefficients of the components were then generated from the fugacity coefficient analog of the MRK equation of state and these coefficients were used together with solubility data to determine the compositions of the coexisting immiscible phases. The tie lines connecting the coexisting phases shift in orientation from nearly parallel to the H₂O-CO₂ binary at low temperatures to almost perpendicular to this binary at high temperatures.  相似文献   

An electrochemical study of Ni²⁺, Co²⁺, and Zn²⁺ ions in melts of composition CaMgSi₂O₆     

Krystyna W. Semkow  Ronald A. Rizzo  Larry A. Haskin  David J. Lindstrom 《Geochimica et cosmochimica acta》1982,46(10):1879-1889

Cyclic voltammetry has been done for Ni²⁺, Co²⁺, and Zn²⁺ in melts of diopside composition in the temperature range 1425 to 1575°C. Voltammetric curves for all three ions excellently match theoretical curves for uncomplicated, reversible charge transfer at the Pt electrode. This implies that the neutral metal atoms remain dissolved in the melt. The reference electrode is a form of oxygen electrode. Relative to that reference assigned a reduction potential of 0.00 volt, the values of standard reduction potential for the ions are $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.32 ± .01}\text{V}$, $\text{E}{}^1\text{(}\text{Co}{}^{\mathrm{2+}}\text{Co}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.45 ± .02}\text{V}$, and $\text{E}{}^1\text{(}\text{Zn}{}^{\mathrm{2+}}\text{Zn}{}^0\text{,}\text{diopside}\text{, 1500°C) = ?0.53 ± .01}\text{V}$. The electrode reactions are rapid, with first order rate constants of the order of 10^?2 cm/sec. Diffusion coefficients were found to be 2.6 × 10^?6 cm²/sec for Ni²⁺, 3.4 × 10^?6 cm²/sec for Co²⁺, and 3.8 × 10^?6 cm²/sec for Zn²⁺ at 1500°C. The value of $\text{E1}$ ($\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0$, diopside) is a linear function of temperature over the range studied, with values of ?0.35 V at 1425°C and ?0.29 V at 1575°C. At constant temperature the value of $\text{E}{}^1\text{(}\text{Ni}{}^{\mathrm{2+}}\text{Ni}{}^0\text{, 1525°C}$) was not observed to vary with composition over the range CaO · MgO · 2SiO₂ to CaO·MgO·3SiO₂ or from 1.67 CaO·0.33MgO·2SiO₂ to 0.5 CaO·1.5MgO·2SiO₂. The value for the diffusion coefficient for Ni²⁺ decreased by an order of magnitude at 1525°C over the compositional range CaO · MgO · 1.25SiO₂ to CaO · MgO · 3SiO₂. This is consistent with a mechanism by which Ni²⁺ ions diffuse by moving from one octahedral coordination site to another in the melt, with the same Ni²⁺ species discharging at the cathode regardless of the SiO₂ concentration in the melt.  相似文献   

Carbon,nitrogen and sulfur in lunar fines 15012 and 15013: abundances,distributions and isotopic compositions     

S. Chang  J. Lawless  M. Romiez  I.R. Kaplan  C. Petrowski  H. Sakai  J.W. Smith 《Geochimica et cosmochimica acta》1974,38(6):853-872

Lunar fines 15012,16 and 15013,3 were analyzed by stepwise pyrolysis and acid hydrolysis as well as complete combustion in oxygen to determine carbon, nitrogen and sulfur. In addition, hydrogen was analysed during pyrolysis as well as during hydrolysis. In the former case, it was released by mineral grains to which it was adsorbed or from cavities within which it had been captured. Hydrogen released during hydrolysis had largely resulted from dissolution of metallic iron.By comparison of the distribution frequencies of C, N, S, H₂ and Fe with ⁴He, considered to have arisen from solar wind contribution, it is concluded that nitrogen and hydrogen have largely a solar origin. Carbon has a significant solar contribution, and metallic iron may have resulted from solar wind interaction with ferrous minerals on the lunar surface. Sulfur probably has a predominantly lunar origin. There is no direct evidence for meteoritic contribution to these samples.Solar wind interaction also has a marked effect on the stable isotope distribution of ¹³C/¹²C, ¹⁵N/¹⁴N, and ³⁴S/³²S. In all cases, the heavy isotope was most enriched in the smallest grain-size fraction. During stepwise pyrolysis, CH₄, CO₂, CO and N₂ were obtained at different temperatures and displayed different isotopic ratios. The carbon fraction most enriched in ¹³C, was CH₄ liberated at 600–800°C with $\text{δ}{}^{13}\text{C = +45.7\%.}$. Between 400 and 600°C, N₂ was liberated with (δ¹⁵N ≈ +119% and at 600–800°C, N₂ was liberated with $\text{δ}{}^{15}\text{N = +75\%.}$ relative to terrestrial atmospheric nitrogen.  相似文献   

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

Eva Marie Hendel  Lincoln S Hollister 《Geochimica et cosmochimica acta》1981,45(2):225-228

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

Methane: An equation of state with application to the ternary system H₂O-CO₂-CH₄     

Gary K Jacobs  Derrill M Kerrick 《Geochimica et cosmochimica acta》1981,45(5):607-614

The following hardsphere modified Redlich-Kwong (HSMRK) equation of state was obtained by least squares fitting to available P-V-T data for methane (P in bars; T in Kelvins; v in cm³ mol^?1; b = 60.00 cm³ mol^?1; R = 83.14 cm³barmol^?1K^?1): $\text{P}\text{RT(1 + y + y}{}^2\text{?y}{}^3\text{v(1?y)}{}^3\text{)}\text{-}\text{c(T) + d(T)}\text{v}\text{+}\text{e(T)}\text{v}{}^2\text{/v(v + b)T}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$$\text{y =}\text{b}\text{4v}$c(T) = 13.403 × 10⁶ + (9.28 × 10⁴)T + 2.7 T²d(T) = 5.216 × 10⁹ ? (6.8 × 10⁶)T + (3.28 × 10³)T²e(T) = (?2.3322 × 10¹¹) + (6.738 × 10⁸)T + (3.179 × 10⁵)T² For the P-T range of experimental data used in the fit (50 to 8600 bars and from 320 to 670 K), calculated volumes and fugacity coefficients for CH₄ relative to experimentally determined volumes and fugacity coefficients have average percent deviations of 0.279 and 1.373, respectively. The HSMRK equation, which predicts linear isochores over a wide P-T range, should yield reasonable estimates of fugacity coefficients for CH₄ to pressures and temperatures well outside the P-T range of available P-V-T data. Calculations for the system H₂O-CO₂-CH₄, using the HSMRK equations for H₂O and CO₂ of Kerrick and Jacobs (1981) and the HSMRK equation for CH₄ of this study, indicate that compared to the binary H₂O-CO₂ system, small amounts of CH₄ in the ternary system H₂O-CO₂-CH₄ slightly increases the activity of H₂O, and significantly decreases the activity of CO₂.  相似文献   

The effect of CO ratio on the condensation of planetary material     

John W. Larimer 《Geochimica et cosmochimica acta》1975,39(3):389-392

The condensation temperatures of refractory silicates and oxides in a gas of cosmic composition are strongly dependent on the $\text{C}\text{O}$ ratio. As the ratio increases from 0.4 to 0.9 (solar ~ cosmic ~ 0.6), condensation temperatures of compounds such as A1₂O₃, Ca₂Al₂SiO₇, MgAl₂O₄, Mg₂SiO₄ and MgSiO₃ decrease by 50–100°. As $\text{C}\text{O}$ increases from 0.9 to 1.0, these temperatures drop an additional 300–400°. Other chemical differences result when $\text{C}\text{O}\text{\$}\text{?}\text{0.9}$ include: a new suite of high temperature minerals appears (graphite, CaS, Fe₃C, SiC and TiN); the reaction CO + 3H₂ → CH₄ + H₂O proceeds to the right at higher temperatures; and iron, whose condensation temperature is unaffected, condenses at higher temperatures than any silicate or oxide.  相似文献   

Pressure dependence ot SrSO₄ solubility     

Neil A. North 《Geochimica et cosmochimica acta》1974,38(7):1075-1081

The solubilities of SrSO₄ in seawater, 0.65 M NaCl and and distilled water were measured as a function of pressure at 2°C. The thermodynamic solubility product was determined from the distilled water measurements and stoichiometric solubility products were determined from the seawater and Nad measurements. The equilibrium quotient for SrSO₄ dissolution at ionic strength of 0.65 was calculated from the NaCl measurements, using the known NaSO₄^? ionpairing association constant. For each of the solubility products values of $\text{Θ V}$ were determined. These experimental values were all $\text{11.0 ± 0.3}\text{ml}$ mole_? lower than the theoretical values based on anhydrous SrSO₄. This difference may be due to the equilibrating solid phase being a hydrated form of SrSO₄.  相似文献   

Melting relationships in the systems CaOCO₂ and MgOCO₂ to 33 kilobars     

Peter J. Wyllie 《Geochimica et cosmochimica acta》1976,40(2):129-132

The melting temperatures of calcite and magnesite in the presence of excess CO₂ have been measured using Ag₂C₂O₄ in sealed capsules m a piston-cylinder apparatus. At 27 kbar, 11.5 wt % CO₂ dissolves in molten CaCO₂, depressing the freezing temperature from 1610 to 1505°C; and 6.5 wt % CO₂ dissolves in molten MgCO₃, depressing the freezing temperature from 1590 to 1510°C. The eutectic between calcite and lime was located at 1385°C at 27 kbar. These and other new results, combined with previously published data, permit completion of PT diagrams for the systems CaO-CO₂ and MgO-CO₂ from 1 bar to 35 kbar. The dissociation curve for each carbonate terminates at an invariant point where melting begins, at 40 bars and 1230°C for CaO-CO₂ and 23 kbar and 1550°C for MgO-CO₂ The differences between the two systems are explained by the different solubilities of CO₂ in the invariant liquids consequent upon the large pressure difference between the locations of these two invariant points. The results show that the temperatures for the beginning of melting of carbonates in the asthenosphere are lowered by about 100°C in the presence of CO₂.  相似文献