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1.
Colin M. Graham Simon M.F. Sheppard Timothy H.E. Heaton 《Geochimica et cosmochimica acta》1980,44(2):353-364
Fractionation factors between epidote minerals and water, and between the AlO(OH) dimorphs boehmite and diaspore and water, have been determined between 150 and 650°C. Small water mineral ratios were used to minimise the effect of incongruent dissolution of epidote minerals. Waters were extracted and analysed directly by puncturing capsules under vacuum. Hydrogen diffusion effects were eliminated by using thick-walled capsules. Exchange rates are very fast between epidote and water (and between boehmite and water), complete exchange taking only minutes above 450°C but several months at 250°C. Exchange between zoisite and water (and between diaspore and water) is very much slower, and an interpolation method was necessary to determine fractionation factors at 450 and below.For the temperature range 300–650°C, the equilibrium fractionation factor (αe) between epidote and water is independent of temperature and Fe content of the epidote, and is given by 1000 In αepidote-H2Oe = ?35.9 ± 2.5, while below 300°C 1000 In , with a ‘cross-over’ estimated to occur at around 185°C. By contrast, zoisite-water fractionations fit the relationship 1000 In .All studied minerals have hydrogen bonding. Fractionations are consistent with the general relationship: the shorter the O-H -- O bridge, the more depleted is the mineral in D.On account of rapid exchange rates, natural epidotes probably acquired their H-isotope compositions at or below 200°C, where fractionations are near or above 0%.; this is in accord with the observation that natural epidotes tend to concentrate D relative to other coexisting hydrous minerals. 相似文献
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3.
The fractionation factors () 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 () approximating the observed fractionation. 相似文献
4.
E.J. Reardon 《Chemical Geology》1976,18(4):309-325
Potentiometric measurements in dilute sodium borate solutions with added alkali earth chlordie salts yield the following expressions for the dissociation constants of alkali earth borate ion pairs from 10 to 50°C:where T is in °K. Enthalpies for the dissociation reactions at 25°C are less than 1 kcal./mole for all the alkali earth borate ion pairs.Values for pK(NaH2BO3°) from 5 to 55°C computed from the experimental data of Owen and King are in good agreement with those determined potentiometrically. The average value from both methods is 0.22 ± 0.1 at 25°C.Application to seawater of computed pK's for MgH2BO3+, CaH2BO3+ and NaH2BO30 yields an apparent dissociation constant for boric acid of 8.73 vs. 8.70 measured by Lyman, 8.68 by Buch and 8.73 by Byrne and Kester. 相似文献
5.
The ionization quotients of aqueous carbon dioxide (carbonic acid) have been precisely determined in NaCl media to 5 m and from 50° to 300°C using potentiometric apparatus previously developed at Oak Ridge National Laboratory. The pressure coefficient was also determined to 250°C in the same media. These results have been combined with selected information in the literature and modeled in two ways to arrive at the best fits and to derive the thermodynamic parameters for the ionization reaction, including the equilibrium constant, activity coefficient quotients, and pressure coefficients. The variation with temperature of the two fundamental quantities and were examined along the saturation vapor pressure curve and at constant density. The results demonstrated again that for reactions with minimal electrostriction changes the magnitudes and variations of and with temperature are small and, in addition, and are approximately independent of salt concentration.The results have also been applied to an examination of the solubility of calcite as a function of pH (in a given NaCl medium) for the neutral to acidic region both for systems with fixed CO2 pressure and systems where the calcium ion concentration equals the concentration of carbon. The pH of saturated solutions of calcite with PCO2 of 12 bars increases from 5.1 to 5.5 between 100° and 300°C. 相似文献
6.
Jrgen Gutzon Larsen 《Lithos》1981,14(4):241-262
Megacrysts and polymineralic fragments of extraordinary diversity from a Tertiary monchiquitic dyke of Ubekendt Ejland comprise three groups: (1) Cr-diopside-fassaitic diopside + olivine, Fo90.5?81.5 + CrAl spinels. (II) Fassaitic salite-ferrisalite + KTi-pargasite-ferropargasite + apatite + AlTi-magnetite, (III) Scapolite + hyalophane + potassium feldspar + nepheline + analcime. By comparison with mineralogy and phase relations in the host rock and experimental data from alkaline rocks the megacrysts are related to a sequence of crystallization from primitive monchiquitic to potassic phonolitic magmas rich in H2O and CO2 at 5–11 kb. Group I megacrysts formed at temperatures of 1300-1150°C and group II between ? bar at the latter temperature. High Pco2 may have stabilized the scapolite in the more evolved liquid and K-feldspar and nepheline began to crystallize at ca. 800°C possibly together with the ferrisalite. 相似文献
7.
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 () 2.57, 1.71, 0.73; Tr-Ta-Qz and Di-Tr-Qz () 4.98, 3.99, 2.21 and 7.29, 5.30, 3.56; WoDi-Qz () 3.30, 3.00, 2.79: Wo-Qz () 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 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
8.
Oxygen isotope exchange between BaSO4 and H2O from 110 to 350°C was studied using 1 m H2SO4-1 m NaCl and 1 m NaCl solutions to recrystallize the barite. The slow exchange rate (only 7% exchange after 1 yr at 110°C and 91% exchange after 22 days at 350°C in 1 m NaCl solution) prompted the use of the partial equilibrium technique. However, runs at 300 and 350°C were checked by complete exchange experiments. The temperature calibration curve for the isotope exchange is calculated giving most weight to the high temperature runs where the partial equilibrium technique can be tested. Oxygen isotope fractionation factors (α) in 1 m NaCl solution (110–350°C), assuming a value of 1.0407 for αCO2H2O at 25°C, are: .These data, when corrected for ion hydration effects in solution (Truesdell, 1974), give the fractionation factors in pure water: .In the 1 m H2SO4-1 m NaCl runs, sulfur isotope fractionation between HSO?4 and BaSO4 is less than the detection limit of 0.4%. A barite-sulfide geothermometer is obtained by combining HSO?4H2S and sulfide-H2S calibration data.Barite in the Derbyshire ore field, U.K., appears to have precipitated in isotopic equilibrium with water and sulfur in the ore fluid at temperatures less than 150°C. At the Tui Mine, New Zealand, the barite-water geothermometer indicates temperatures of late stage mineralization in the range 100–200°C. A temperature of 350 ± 20°C is obtained from the barite-pyrite geothermometer at the Yauricocha copper deposit, Peru, and oxygen isotope analyses of the barite are consistent with a magmatic origin for the ore fluids. 相似文献
9.
The solubility of rutile has been determined in a series of compositions in the K2O-Al2O3-SiO2 system ( + Al2O3) = 0.38–0.90), and the CaO-Al2O3-SiO2 system (). Isothermal results in the KAS system at 1325°C, 1400°C, and 1475°C show rutile solubility to be a strong function of the ratio. For example, at 1475°C the amount of TiO2 required for rutile saturation varies from 9.5 wt% () to 11.5 wt% () to 41.2 wt% (). In the CAS system at 1475°C, rutile solubility is not a strong function of . The amount of TiO2 required for saturation varies from 14 wt% () to 16.2 wt% ().The solubility changes in KAS melts are interpreted to be due to the formation of strong complexes between Ti and K+ in excess of that needed to charge balance Al3+. The suggested stoichiometry of this complex is K2Ti2O5 or K2Ti3O7. In CAS melts, the data suggest that Ca2+ in excess of A13+ is not as effective at complexing with Ti as is K+. The greater solubility of rutile in CAS melts when is less than 0.54 compared to KAS melts of equal ratio results primarily from competition between Ti and Al for complexing cations (Ca vs. K).TiKβ x-ray emission spectra of KAS glasses () with 7 mole% added TiO2, rutile, and Ba2TiO4, demonstrate that the average Ti-O bond length in these glasses is equal to that of rutile rather than Ba2TiO4, implying that Ti in these compositions is 6-fold rather than 4-fold coordinated. Re-examination of published spectroscopic data in light of these results and the solubility data, suggests that the 6-fold coordination polyhedron of Ti is highly distorted, with at least one Ti-O bond grossly undersatisfied in terms of Pauling's rules. 相似文献
10.
The spectrophotometric measurements of chloro complexes of lead in aqueous HCl, NaCl, MgCl2 and CaCl2 solutions at 25°C have been analyzed using Pitzer's specific interaction equations. Parameters for activity coefficients of the complexes PbCl+, PbCl20 and PbCl3? have been determined for the various media. Values of , and were obtained for the cumulative formation constants. []. These values are in reasonable agreement with literature data. The Pitzer parameters for the PbCl ion pairs in various media were used to calculate the speciation of Pb2+ in an artificial seawater solution. 相似文献
11.
J.R Holloway 《Geochimica et cosmochimica acta》1973,37(3):651-666
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 () ranged from 1.0 to 0.2.At P < 4 kbar the stability temperature (T) of pargasite decreases with decreasing at constant P. Above P ? 4 kbar stability T increases as is decreased below one, passes through a T maximum and then decreases with a further decrease in . This behavior is due to a decrease in the H2O content of the silicate liquid as decreases. The magnitude of the T maximum increases from about 10°C (relative to the stability T for ) at P = 5 kbar to about 30°C at P = 8 kbar, and the position of the maximum shifts from at P = 5 kbar to at P = 8 kbar.The H2O content of liquid coexisting with pargasite has been estimated as a function of 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 at high P and T, hornblende can be an important phase in igneous processes even at relatively low H2O fugacities. 相似文献
12.
Solubility product of galena at 298°K: A possible explanation for apparent supersaturation in nature
The synthetic chelating agent ethylenediaminetetraacetic acid (EDTA) has been used to evaluate the stoichiometric solubility product of galena (PbS) at 298°K: This method circumvents the possible uncertainties in the stoichiometry and stability of lead sulfide complexes. At infinite dilution, , and at an ionic strength corresponding to seawater (), . Using the value of at infinite dilution, and the free energies of formation of HS? and Pb2+ at 298°K (literature values), the free energy of formation of PbS at 298°K is computed to be . Galena is shown to be more than two orders of magnitude more soluble than indicated by calculations based on previous thermodynamic data. 相似文献
13.
Diffusion of ions in sea water and in deep-sea sediments 总被引:3,自引:0,他引:3
Sandra Gregory 《Geochimica et cosmochimica acta》1974,38(5):703-714
The tracer-diffusion coefficient of ions in water, Dj0, and in sea water, , differ by no more than zero to 8 per cent. When sea water diffuses into a dilute solution of water, in order to maintain the electro-neutrality, the average diffusion coefficients of major cations become greater but of major anions smaller than their respective or Dj0 values. The tracer diffusion coefficients of ions in deep-sea sediments, Dj,sed., can be related to by , where θ is the tortuosity of the bulk sediment and a a constant close to one. 相似文献
14.
Ralph Kretz 《Geochimica et cosmochimica acta》1982,46(3):411-421
Differences in the chemical composition of metamorphic and igneous pyroxene minerals may be attributed to a transfer reaction, which determines the Ca content of the minerals, and an exchange reaction, which determines the relative Mg:Fe2+ ratios. Natural data for associated Ca pyroxene (Cpx) and orthopyroxene (Opx) or pigeonite are combined with experimental data for Fe-free pyroxenes, to produce the following equations for the Cpx slope of the solvus surface: , and the following equation for the temperature-dependence of the Mg-Fe distribution coefficient: , where T is absolute temperature, X is , [Ca] is in Cpx, and KD is the distribution coefficient, defined as .The transfer and exchange equations form useful temperature indicators, and when applied to 9 sets of well-studied rocks, yield pairs of temperatures that are in good agreement. For example, temperatures obtained for the Bushveld Complex are 1020°C (solvus equation) and 980°C (exchange equation), based on 7 specimens. The uncertainty in these numbers, due to precision and accuracy errors, is estimated to be ±60°. 相似文献
15.
A.E. Beswick 《Geochimica et cosmochimica acta》1973,37(2):183-208
K and Rb distributions between aqueous alkali chloride vapour phase (0.7 molar) and coexisting phlogopites and sanidines have been investigated in the range 500 to 800°C at 2000 kg/cm2 total pressure.Complete solid solution of RbMg3AlSi3O10(OH)2 in KMg3AlSi3O10(OH)2 exists at and above 700°C. At 500°C a possible miscibility gap between approximately 0.2 and 0.6 mole fraction of the Rb end-member is indicated.Only limited solid solution of Rb AlSi3O8 in KAlSi3O8 has been found at all temperatures investigated.Distribution coefficients, expressed as in solid/(Rb/K) in vapour, are appreciably temperature-dependent but at each temperature are independent of composition for low Rb end-member mole fractions in the solids. The determined values and their approximate Rb end-member mole fraction () ranges of constancy are summarized as follows: (°C)
(°C)T | ||||
500 | 0–0.2 | 0–0.07 | ||
700 | 0–0.2 | 0–0.1 | ||
800 | 0–0.2 | 0–0.1 |