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1.
The stability of the amphibole pargasite [NaCa2Mg4Al(Al2Si6))O22(OH)2] in the melting range has been determined at total pressures (P) of 1.2 to 8 kbar. The activity of H2O was controlled independently of P by using mixtures of H2O + CO2 in the fluid phase. The mole fraction of H2O in the fluid (XH2O1fl) ranged from 1.0 to 0.2.At P < 4 kbar the stability temperature (T) of pargasite decreases with decreasing XH2O1fl at constant P. Above P ? 4 kbar stability T increases as XH2O1fl is decreased below one, passes through a T maximum and then decreases with a further decrease in XH2O1fl. This behavior is due to a decrease in the H2O content of the silicate liquid as XH2O1fl decreases. The magnitude of the T maximum increases from about 10°C (relative to the stability T for XH2O1fl= 1) at P = 5 kbar to about 30°C at P = 8 kbar, and the position of the maximum shifts from XH2O1fl ? 0.6 at P = 5 kbar to XH2O1fl? 0.4 at P = 8 kbar.The H2O content of liquid coexisting with pargasite has been estimated as a function of XH2O1fl at 5 and 8 kbar P, and can be used to estimate the H2O content of magmas. Because pargasite is stable at low values of XH2O1fl at high P and T, hornblende can be an important phase in igneous processes even at relatively low H2O fugacities.  相似文献   

2.
The partial molal volume of silicic acid (V?(Si(OH)4)) in 0.725 M NaCl at 1°C was calculated from the measured volume change (ΔV?n) due to the neutralization of anhydrous sodium metasilicate with HCl and the V?(HCl) and V?(NaCl) obtained from the literature. V?(Si(OH)4) = 59.0 cm3mol ? 1, determined under experimental conditions of pH = 2.2, compares favorably with V?(Si(OH)4) = 58.9 cm3 mol?1 calculated from the measured volume change due to the hydrolysis of the meta-silicate salt at pH = 11 and from the partial molal volume due to electrostriction (V?elect) of water by charged Si species present in the solution at the high pH. This agreement lends support to a semiempirical model for calculating V?elect in developed by Millero (1969). V?(NaOH) = ? 5.45 cm3 mol?1 in 0.725 M NaCl needed for this calculation was also determined in this work. The rate of polymerization of Si(OH)4 at 1°C was monitored to insure that the monomer Si(OH)4 was the main Si species present during the determination of V?(Si(OH)4) by neutralization of the alkali silicate. V?(Si(OH)4) determined in this study compares favorably with the value calculated from high pressure solubility measurements.  相似文献   

3.
Direct Pco2 measurements on water samples from several CO2-charged warm springs are significantly higher than Pco2 values calculated from field pH and alkalinity (and other constituents). In addition, calcite saturation indices calculated from field pH and solution composition indicated supersaturation in samples which, on the basis of hydrogeologic concepts, should be near saturation or undersaturated. We attribute these discrepancies to uncertainties in field pH, resulting from CO2 outgassing during pH measurement. Because samples for direct Pco2 measurement can be taken with minimal disturbance to the water chemistry, we have used the measured Pco2 to back calculate an estimate of the field pH and the carbon isotopic composition of the water before outgassing. By reconstructing water chemistry in this way, we find generally consistent grouping of δ13C, pH, and degree of calcite saturation in samples taken from the same source at different times, an observation which we expect based on our understanding of the hydrogeology and geochemistry of the ground-water systems. This suggests that for very careful geochemical work, particularly on ground-waters much above ambient temperature, Pco2 measurements may provide more information on the system and a better estimate of its state of saturation with respect to carbonate minerals than can field measurements of pH.  相似文献   

4.
A thermodynamic model for concentrated brines has been developed which is capable of predicting the solubilities of many of the common evaporite minerals in chloro-sulfate brines at 25°C and 1 atm. The model assumes that the behaviour of the mean stoichiometric ionic activity coefficient in mixtures of aqueous electrolytes can be described by the Scatchard deviation function and Harned's Rule. In solutions consisting of one salt and H2O, the activity coefficient is described by the expression logλ4plusm;=-|z+z? √ 1/c1+a?B √ I) + 2(V+V?/v)Bi?l where a? and B? salt specific parameters obtained from data regression. In a mixture of n electrolytes and H2O, B? for the ith component is given by Bi?i=B i?i+σ αijyj where αij is a (constant) mixing parameter characterizing the interaction of the i and j components and yj is the ionic strength fraction of the jth component. The activity of H2O is obtained from a Gibbs-Duhem integration and does not require any additional parameters or assumptions. In this study, parameters have been obtained for the systems NaCl-KCl-MgCl2-CaCl2-H2O and NaCl-MgSO4-H2O at 25°C and 1 atm. Computed solubility curves and solution compositions predicted for invariant points in these systems agree well with the experimental data. The model is flexible and easily extended to other systems and to higher temperatures.  相似文献   

5.
Mineral-aqueous solution equilibria for the assemblages talc-quartz, tremolite-talc-quartz, diopside-tremolite-quartz, wollastonite-diopside-quartz and wollastonite-quartz have been studied at 2 kb total pressure, 500° to 700°C and chloride concentrations from 0.03 to 6.0 molal. Most work was at 1 m chloride. Both buffered and unbuffered data were obtained and a recalibration of the Ag-AgCl buffer is presented. Log equilibrium quotients at 500°, 600° and 700°C are respectively: Ta-Qz (mMgCl2mHCl2) 2.57, 1.71, 0.73; Tr-Ta-Qz and Di-Tr-Qz (mCaCl2mMgCl2mHCl2) 4.98, 3.99, 2.21 and 7.29, 5.30, 3.56; WoDi-Qz (mCaCl2mMgCl2) 3.30, 3.00, 2.79: Wo-Qz (mCaCl2mHCl2) 5.15, 3.95, 2.68. Mineral stability fields plotted in terms of these concentration data more tangibly represent the compositional character of real systems and the mass transfer capabilities of their fluids than do the analogous theoretical activity diagrams.Overall dissociation constants of MgCl2 and CaCl2 were calculated from the experimental data using the calculated ionic activity constants for the reactions and the established dissociation constants of HCl. The negative log values are respectively: 3.88. 6.63, 9.20 for CaCl2 and 4.60, 7.54, 10.37 for MgCl2 at 500°, 600° and 700°C, 2 kb. The Ca values are about an order of magnitude more positive than the conductance-derived values by Frantz and Marshall (1982).The phase relations developed in this study have application to the genesis of talc, tremolite, and diopside-bearing assemblages in some regional metamorphic rocks, but more specifically to the calcsilicate skarn assemblages of many metasomatic aureoles. The equilibrium fluids are characterized by high concentrations of Ca relative to Mg and increasing CaMg ratios with decreasing temperatures. The stability fields of talc, tremolite, and quartz expand relative to those of diopside and wollastonite with decreasing temperature, hence their more common appearance as retrograde products in skarn systems.  相似文献   

6.
Compositional differences between granulite facies rocks and equivalent amphibolite facies rocks and the observation of CO2-rich fluid inclusions in granulites, have led to the suggestion that CO2 must play a role in modifying the composition of deep continental crust. How CO2 effects this change has remained unclear. Using the thermodynamic properties of aqueous ions in a fluid of evolving CO2H2O ratio, it is possible to model the incongruent dissolution of feldspars under conditions appropriate for granulite facies metamorphism. The results demonstrate that dissolution will be strongly enhanced at high CO2H2O ratios, with ion solubilities being Na+ >K+ ? Ca++. This enhancement is compatible with the reported compositional contrasts between granulite and amphibolite facies rock, but requires large fluid volumes.To test the dissolution model, a detailed field and petrologic study was conducted in a well exposed granulite facies terrane in West Greenland. Strong correlation between fluid composition and bulk rock chemistry can be documented; CO2-rich regions contain rocks which consistently have low aNa2OaCaO ratios, while H2O-rich regions consistently have high aNa2OaCaO ratios. Magnetite rims on sulfide grains are ubiquitous in high ?Co2 regions and are absent in high ?H2O regions, and they provide evidence that CO2 was introduced into the region. These correlations and observations are predictable from the properties of the dissolution process. These considerations, along with observations regarding graphite petrogenesis, provide strong arguments that the total fluid volume interacting with the rock during metamorphism was very large, in some cases equaling or exceeding total rock volume. Such large fluid volumes can lead to significant compositional modification of the crust, and will mask the original protolith chemistry. Such processes should lead to Ca- and Al-enriched, Na-, K-, S- and Si-depleted residues in the deep crust.  相似文献   

7.
Auger electron spectroscopy has been used to study K-feldspar that has been reacted with both aqueous 10% HF and a 50% mixture of a 10% HF/0.1 N H2SO4 solution. In the feldspar/HF system, the resulting feldspar surface was shown to have been fluorinated; depth profiling, using argon ion sputtering, showed the fluorination to have occurred substantially into the mineral bulk. In the feldspar/ HFH2SO4 system, the resulting surface contained both fluorine and sulfur. The fluorination had again penetrated into the bulk, but the sulfur could be removed with mild argon ion sputtering. The AlF signal ratio was much lower on the feldspar surface treated with the 10% HF/0.1 N H2SO4 solution than the feldspar surface treated with the weaker 10% HF acid solution.  相似文献   

8.
While gibbsite and kaolinite solubilities usually regulate aluminum concentrations in natural waters, the presence of sulfate can dramatically alter these solubilities under acidic conditions, where other, less soluble minerals can control the aqueous geochemistry of aluminum. The likely candidates include alunogen, Al2(SO4)3 · 17H2O, alunite, KAl3(SO4)2(OH)6, jurbanite, Al(SO4)(OH) · 5H2O, and basaluminite, Al4(SO4)(OH)10 · 5H2O. An examination of literature values shows that the log Ksp = ?85.4 for alunite and log Ksp = ?117.7 for basaluminite. In this report the log Ksp = ?7.0 is estimated for alunogen and log Ksp = ?17.8 is estimated for jurbanite. The solubility and stability relations among these four minerals and gibbsite are plotted as a function of pH and sulfate activity at 298 K. Alunogen is stable only at pH values too low for any natural waters (<0) and probably only forms as efflorescences from capillary films. Jurbanite is stable from pH < 0 up to the range of 3–5 depending on sulfate activity. Alunite is stable at higher pH values than jurbanite, up to 4–7 depending on sulfate activity. Above these pH limits gibbsite is the most stable phase. Basaluminite, although kinetically favored to precipitate, is metastable for all values of pH and sulfate activity. These equilibrium calculations predict that both sulfate and aluminum can be immobilized in acid waters by the precipitation of aluminum hydroxysulfate minerals.Considerable evidence supports the conclusion that the formation of insoluble aluminum hydroxy-sulfate minerals may be the cause of sulfate retention in soils and sediments, as suggested by Adams and Rawajfih (1977), instead of adsorption.  相似文献   

9.
CaCO3Ca(OH)2CaS serves as a model system for sulfide solubility in carbonatite magmas. Experiments at 1 kbar delineate fields for primary crystallization of CaCO3, Ca(OH)2 and CaS. The three fields meet at a ternary eutectic at 652°C with liquid composition (wt%): CaCO3 = 46.1%, Ca(OH)2 = 51.9%, CaS = 2.0%. Two crystallization sequences are possible for liquids that precipitate calcite, depending upon whether the liquid is on the low-CaS side, or the high-CaS side of the line connecting CaCO3 to the eutectic liquid. Low-CaS liquids precipitate no sulfide until the eutectic temperature is reached leading to sulfide enrichment. The higher-CaS liquids precipitate some sulfide above the eutectic temperature, but the sulfide content of the melt is not greatly depleted as the eutectic temperature is approached. Theoretical considerations indicate that sulfide solubility in carbonate melts will be directly proportional to ?S212 and inversely proportional to ?O212; it also is likely to be directly proportional to melt basicity, defined here by aCO32??CO2. A strong similarity exists in the processes which control sulfide solubility in carbonate and in silicate melts. By analogy with silicates, ferrous iron, which was absent in our experiments, may also exert an important influence on sulfide solubility in natural carbonatite magmas.  相似文献   

10.
Significant amounts of SO42?, Na+, and OH? are incorporated in marine biogenic calcites. Biogenic high Mg-calcites average about 1 mole percent SO42?. Aragonites and most biogenic low Mg-calcites contain significant amounts of Na+, but very low concentrations of SO42?. The SO42? content of non-biogenic calcites and aragonites investigated was below 100 ppm. The presence of Na+ and SO42? increases the unit cell size of calcites. The solid-solutions show a solubility minimum at about 0.5 mole percent SO42? beyond which the solubility rapidly increases. The solubility product of calcites containing 3 mole percent SO42? is the same as that of aragonite. Na+ appears to have very little effect on the solubility product of calcites. The amounts of Na+ and SO42? incorporated in calcites vary as a function of the rate of crystal growth. The variation of the distribution coefficient (D) of SO42? in calcite at 25.0°C and 0.50 molal NaCl is described by the equation D = k0 + k1R where k0 and k1 are constants equal to 6.16 × 10?6 and 3.941 × 10?6, respectively, and R is the rate of crystal growth of calcite in mg·min?1·g?1 of seed. The data on Na+ are consistent with the hypothesis that a significant amount of Na+ occupies interstitial positions in the calcite structure. The distribution of Na+ follows a Freundlich isotherm and not the Berthelot-Nernst distribution law. The numerical value of the Na+ distribution coefficient in calcite is probably dependent on the number of defects in the calcite structure. The Na+ contents of calcites are not very accurate indicators of environmental salinities.  相似文献   

11.
The partitioning of germanium between forsterite (Fo) and liquids in the diopside-anorthiteforsterite join was investigated by electron microprobe analysis of Ge-doped samples equilibrated at 1300°–1450°C. Germanium is somewhat incompatible in Fo relative to the haplobasaltic melts, with a grand mean for all simple partition coefficients (DFo-lGe) of 0.68 ± 0.06. For the melt composition range studied, DFo-lGe is virtually constant in isothermal series of experiments, and shows only minor overall temperature dependence. The exchange reaction partition coefficient KD = (Mg2GeO4)Fo(SiO2)l(Mg2SiO4)Fo(GeO2)l] is near unity in all cases, with a grand mean of 0.93 ± 0.11. One exploratory run at 20 kbar yielded a distinctly lower partition coefficient (DFo-lGe = 0.54 ± 0.04), which confirms the negative pressure dependence predicted by the thermodynamics of Ge ai Si exchange.These new data indicate that absolute Ge enrichment must occur in terrestrial magmas undergoing olivine fractionation, while GeSi remains nearly constant.  相似文献   

12.
The 13C12C fractionation factors (CO2CH4) 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 (CO2HCH3) approximating the observed CO2CH4 fractionation.  相似文献   

13.
A new technique for the determination of intrinsic oxygen fugacities (?O2's) of single and polyphase geological samples with solid ZrO2, oxygen-specific electrolytes is described. Essentially the procedure involves isolating the emf signal from the sample from that unavoidably imposed by the residual atmosphere inside the sample-bearing sensor. By varying the ?O2 of the residual atmosphere, it is possible to determine a ‘plateau’ value of constant ?O2 recorded from the sensor which represents a reversed intrinsic ?O2 measurement for the sample alone, and where the extent of the plateau reflects the innate buffering capability of the sample. A measure of the precision and accuracy of the data obtained is the fact that identical ?O2 values are obtained whether on a heating or cooling cycle of the sample + compatible atmosphere system.These techniques have been applied to measurements of the intrinsic ?O2 of spinels from peridotites and megacryst assemblages from Australia, West Germany and the U.S.A. Oxidation states range from ~- 0.25 log10 units more oxidized to 1 log10 unit more reduced than the iron-wüstite (IW) buffer. The overall reduced nature of the spinels and the range of ?O2's obtained are striking features of the data. One implication of the results is that the majority of mantle-derived magmas are initially highly reduced, and the relatively oxidized values observed at surface (~- 4–5 log10 orders more oxidized than IW) reflect late-stage alteration, perhaps by H2 loss (Sato, 1978).  相似文献   

14.
Electron microprobe analyses of the spinel mineral group, ilmenite and rutile have been carried out on part of the Luna 20 soil sample. The spinel group shows an almost continuous trend from MgAl8O4 to FeCr2O4 and a discontinuous trend from FeCr2O4 to Fe2TiO4. Well defined non-linear relationships exist within the spinel group for Fe-Mg substitution, for divalent (FeOFeO + MgO) versus trivalent (Cr2O3Cr2O3 + A12O3), and for divalent versus TiO2TiO2 + A12O3 + Cr2O3. For Cr-Al substitution the relationship is linear and is negative for Mg-rich spinel and positive for Fe-Ti rich spinel. In general a combination of aluminous-rich chromite and ulvöspinel in the Luna 16 samples, combined with the chromian-pleonaste in Apollo 14 define comparable major compositional trends to those observed in Luna 20. Ilmenite is present in trace amounts. It is exsolved from pleonaste and pyroxene, is present in subsolidusreduced ulvöspinel and has undergone reequilibration to produce oriented intergrowths of chromite + rutile. Primary ilmenite is among the most magnesian-rieh (6 wt.% MgO) yet found in the lunar samples. The high MgO, inferred high Cr2O3 concentrations and the iron content of rutile (2.5 wt.% FeO) suggest crystallization at high temperatures and pressures for some components of the Luna 20 soil.  相似文献   

15.
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 N2(N2+ CO2) 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) N2(N2 + CO2) > 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) 0,20 < N2(N2 + CO2) ? 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) N2(N2 + CO2) ? 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   

16.
If the temperature of ground water is below 75°C and the partial pressure of CO2 in the aquifer is above 10?4 atm, a chemical steady-state between water and felsic rocks (rather than chemical equilibrium) may be maintained. The temperature of water in the aquifer may be estimated using a modified form of the Na-K-Ca geothermometer from, I = ?1.36 ?0.253 log Pco2. where the departure of the steady-state from equilibrium, I, is a function of Pco2: I = ?1.36 ?0.253 log Pco2.  相似文献   

17.
The chemical composition of gas mixtures emerging in thermal areas can be used to evaluate the deep thermal temperatures. Chemical analyses of the gas compositions for 34 thermal systems were considered and an empirical relationship developed between the relative concentrations of H2S, H2, CH4 and CO2 and the reservoir temperature. The evaluated temperatures can be expressed by: t°C = 24775α + β + 36.05 ?273 where α = 2 logCH4CO2 ?log H2CO2?3 log H2SCO2 (concentrations in % by volume) and β = 7 logPco2  相似文献   

18.
Equations are developed for calculating the density of aluminosilicate liquids as a function of composition and temperature. The mean molar volume at reference temperature Tr, is given by Vr = ∑XiV?oi + XAV?oA, where the summation is taken over all oxide components except A12O3, X stands for mole fraction, V?oi terms are constants derived independently from an analysis of volume-composition relations in alumina-free silicate liquids, and V?oA is the composition-dependent apparent partial molar volume of Al2O3. The thermal expansion coefficient of aluminosilicate liquids is given by α = ∑Xi\?gaio + XA\?gaAo, where \?gaio terms are constants independent of temperature and composition, and \?gaoA is a composition-dependent term representing the effect of Al2O3 on the thermal expansion. Parameters necessary to calculate the volume of silicate liquids at any temperature T according to V(T) = Vrexp[α(T-Tr)], where Tr = 1400°C have been evaluated by least-square analysis of selected density measurements in aluminosilicate melts. Mean molar volumes of aluminosilicate liquids calculated according to the model equation conform to experimentally measured volumes with a root mean square difference of 0.28 ccmole and an average absolute difference of 0.90% for 248 experimental observations. The compositional dependence of V?oA is discussed in terms of several possible interpretations of the structural role of Al3+ in aluminosilicate melts.  相似文献   

19.
20.
Light hydrocarbon (C1-C3) concentrations in the water from four Red Sea brine basins (Atlantis II, Suakin, Nereus and Valdivia Deeps) and in sediment pore waters from two of these areas (Atlantis II and Suakin Deeps) are reported. The hydrocarbon gases in the Suakin Deep brine (T = ~ 25°C, Cl? = ~ 85‰, CH4 =~ 711) are apparently of biogenic origin as evidenced by C1(C2 + C3) ratios of ~ 1000. Methane concentrations (6–8 μl/l) in Suakin Deep sediments are nearly equal to those in the brine, suggesting sedimentary interstitial waters may be the source of the brine and associated methane.The Atlantis II Deep has two brine layers with significantly different light hydrocarbon concentrations indicating separate sources. The upper brine (T = ~ 50°C, Cl? = ~ 73‰, CH4 = ~ 155 μl/l) gas seems to be of biogenic origin [C1(C2 + C3) = ~1100], whereas the lower brine (T = ~ 61°C, Cl? = ~ 155‰, CH4 = ~ 120μl/l) gas is apparently of thermogenic origin [C1(C2 + C3) = ~ 50]. The thermogenic gas resulting from thermal cracking of organic matter in the sedimentary column apparently migrates into the basin with the brine, whereas the biogenic gas is produced in situ or at the seawater-brine interface. Methane concentrations in Atlantis II interstitial waters underlying the lower brine are about one half brine concentrations; this difference possibly reflects the known temporal variations of hydrothermal activity in the basin.  相似文献   

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