Subsolidus and melting relations for the join CaCO3-MgCO3 at 10 kbar     

Alan P Byrnes  Peter J Wyllie 《Geochimica et cosmochimica acta》1981,45(3):321-328

Mixtures of pure dry CaCO₃ and MgCO₃ were reacted at 10 kbar in a piston-cylinder apparatus. Solidus and liquidus boundaries were delineated by interpretation of quenched textures. X-ray determined compositions of quenched carbonates are not a reliable guide to the phase relations. The binary melting loop for CaCO₃-MgCO₃ extends from CaCO₃ at 1460°C through a liquidus minimum near 30 wt% MgCO₃ and 1075°C, and it is terminated at the incongruent melting reaction for dolomite solid solution at 1125° C (liquid with 32 wt% MgCO₃) Magnesite solid solution dissociates at 1090°C to produce dolomite + periclase + CO₂, truncating the dolomite-magnesite solvus. The 10 kb liquidus minimum at 1075°C and 30 wt% MgCO₃ occurs at lower temperature and higher $\text{Ca}\text{Mg}$ ratio than the 27 kbar liquidus minimum at 1290°C and 38 wt% MgCO₃. This relationship suggests that the first liquid produced by melting of a carbonate-bearing peridotite has increasing $\text{Mg}\text{Ca}$ ratio with increasing pressure. These phase relations provide part of the framework required to trace paths of crystallization of kimberlite and carbonatite magmas.  相似文献   

The stability of CaCO₃·6H₂O (ikaite)     

Gregg Marland 《Geochimica et cosmochimica acta》1975,39(1):83-91

Experimental runs were made in cold-seal pressure vessels using synthetic CaCO₈·6H₂O, calcite and aragonite as starting materials. The reaction CaCO₃·6H₂O (ikaite) ? CaCO₃ (calcite I) + 6H₂O was reversed across its metastable extension into the aragonite stability field and the phase boundary is defined by brackets at 4.14kb, 14.3°C and 2.96 kb, ?3.0°C. An invariant point for CaCO₃·6H₂O, calcite I, aragonite and water thus occurs at about 3.02 kb and ?2.0°C. No other reaction could be reversed. Calculations based on the equilibrium phase boundary between calcite and ikaite and the available thermochemical data for calcite and water yield the stadard free energy of formation, standard enthalpy of formation and third law entropy of CaCO₃·6H₂O at 25°C and 1 bar total pressure; ?607.3 kcal/mole, ?705.8 kcal/mole, and 88.4 cal/deg mole, respectively.  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   

Calcite-dolomite geothermometry for iron-bearing carbonates     

M. J. Bickle  R. Powell 《Contributions to Mineralogy and Petrology》1977,59(3):281-292

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Structure of mineral glasses—III. NaAlSi₃O₈ supercooled liquid at 805°C and the effects of thermal history     

Mark Taylor  Gordon E. Brown  Philip M. Fenn 《Geochimica et cosmochimica acta》1980,44(1):109-117

The distribution of interatomic distances in amorphous NaAlSi₃O₈ has been determined at 805°C by X-ray radial distribution analysis to investigate structural differences between the glass (T < 763°C) and the supercooled liquid (763°C < T < 1118°C). Except for slight differences attributable to thermal expansion, no significant changes were observed. The sample crystallized during the course of the experiment, but at least one crystal-free data set was obtained. The transition from the inferred six-membered ring structure of the supercooled liquid to the four-membered ring structure of the crystal was clearly visible in radial distribution function (RDF's) determined before and after crystallization.RDF's were also determined at 25°C for two NaAlSi₃O₈ glasses with different histories. The first was derived from a melt that had been cooled slowly from 1600 to 32°C above the melting point (T_f = 1118°C) to detect possible repolymerization to a more ‘crystal-like’ structure as the melt approached T_f. The second glass was prepared by holding a single crystal of Amelia albite at 50°C above T_f to see if the crystalline four-membered ring structure was preserved in melts at temperatures just above the liquidus. No significant differences were observed between these two RDF's and one obtained from a glass quenched from 1800°C. These results suggest that in addition to the destruction of formation of a periodic structure, melting and crystallization in NaAlSi₃O₈ also involves a repolymerization of tetrahedra. This would explain the observed kinetic barrier to melting and crystallization in the anhydrous system and the catalytic effect of small amounts of water or alkali oxide.  相似文献   

Activity coefficients of MgCO^o₃ and CaSO^o₄ ion pairs as a function of ionic strength     

Eric J Reardon  Donald Langmuir 《Geochimica et cosmochimica acta》1976,40(5):549-554

Based on potentiometric data and gypsum solubility in mixed salt solutions, respectively, the activity coefficients of MgCO^o₃ and CaSO^o₄ ion pairs decrease with ionic strength (I) at 25°C. Computed γ's for the ion pairs fit the empirical equation log γ_i = ? BI. B coefficients of 0.63 ±0.10 for MgCO^o₃ and 0.45 ± 0.15 for CaSO^o₄ are obtained from linear regression of log γ_i values vs I between 0.04 and 0.6 molal. Assumptions that the activity coefficients of these neutral ion pairs equal unity or are approximated by the Setchenow expression (log γ_i = kI) are therefore invalid at moderate ionic strengths. Log γ_i = ? BI is the same general form as the equation of Kirkwood (Chem. Rev.24, 233–251, 1939) for neutral dipoles.  相似文献   

Ternary Ca–Fe–Mg carbonates: subsolidus phase relations at 3.5 GPa and a thermodynamic solid solution model including order/disorder     

E.?FranzolinEmail author  M.?W.?Schmidt  S.?Poli 《Contributions to Mineralogy and Petrology》2011,161(2):213-227

Subduction carries atmospheric and crustal carbon hosted in the altered oceanic crystalline basement and in pelagic sediments back into the mantle. Reactions involving complex carbonate solid solutions(s) lead to the transfer of carbon into the mantle, where it may be stored as graphite/diamond, in fluids or melts, or in carbonates. To constrain the thermodynamics and thus reactions of the ternary Ca–Mg–Fe carbonate solid solution, piston cylinder experiments have been performed in the system CaCO₃–MgCO₃–FeCO₃ at a pressure of 3.5 GPa and temperatures of 900–1,100°C. At 900°C, the system has two miscibility gaps: the solvus dolomite–calcite, which closes at X _MgCO3 ~0.7, and the solvus dolomite–magnesite, which ranges from the Mg to the Fe side of the ternary. With increasing temperature, the two miscibility gaps become narrower until complete solid solutions between CaCO₃–Ca_0.5Mg_0.5CO₃ is reached at 1,100°C and between CaCO₃–FeCO₃ at 1,000°C. The solvi are characterized by strong compositional asymmetry and by an order–disorder mechanism. To deal with these features, a solid solution model based on the van Laar macroscopic formalism has been calculated for ternary carbonates. This thermodynamic solid solution model is able to reproduce the experimentally constrained phase relations in the system CaCO₃–MgCO₃–FeCO₃ in a broad P–T range. To test our model, calculated phase equilibria were compared with experiments performed in carbonated mafic protolithes, demonstrating the reliability of our solid solution model at pressures up to 6 GPa in complex systems.  相似文献   

Genetic link between saline and carbonatitic mantle fluids: The system NaCl-CaCO3-MgCO3 ± H2O ± Fe0 at 6 GPa     

《地学前缘(英文版)》2022,13(6):101431

Melt inclusions in kimberlitic minerals and diamonds indicate that chlorides are important constituents of mantle carbonatite melts. Besides, alkaline chlorides are important constituents of saline high-density fluids (HDFs) found in diamonds from kimberlites and placers around the world. Continuous compositional variations suggest that saline and carbonatitic HDFs could be genetically linked. However, the essence of this link remains unclear owing to the lack of data on phase relations in the chloride-carbonate systems under pressure. Here we studied subsolidus and melting phase relations in the system NaCl–CaCO₃–MgCO₃ at 6 GPa and 1000–1600 °C using a Kawai-type multianvil press. We found that at 1000 °C, subsolidus assemblage consists of halite, magnesite, and aragonite. At higher temperatures, the stabilization of dolomite splits the subsolidus area into two partial ternary fields: halite + magnesite + dolomite and halite + dolomite + aragonite. The minimum on the liquidus surface corresponds to the halite-dolomite-aragonite ternary eutectic, situated at 1100 °C. The eutectic melt has Ca# 89 and contains 30 wt.% NaCl (26 mol% 2NaCl). The system has two ternary peritectics: halite + dolomite = magnesite + liquid located near the ternary eutectic and magnesite + dolomite = Mg-dolomite + liquid situated between 1300 and 1400 °C. Although under dry conditions incipient melting yields carbonate-dominated melt, the addition of water facilitates the fusion of NaCl and expands the liquid field to NaCl-rich compositions with up to 70 wt.% NaCl. The obtained results favor the idea that hydrous saline melts/fluids (brines) found as inclusions in diamonds could be a lower temperature derivative of mantle carbonatite melts and disagree with the hypothesis on chloride melt generation owing to the chloride-carbonate liquid immiscibility since no such immiscibility was established. We also studied the interaction of the NaCl–CaCO₃–MgCO₃ system with iron metal and found that carbonate reduction produces C-bearing species (Fe⁰, Fe-C melt, Fe₃C, Fe₇C₃, C⁰) and wüstite containing Na₂O, CaO, and MgO. Besides, a carbonate chloride compound, Ca₂Cl₂CO₃, was established among the reaction products. The interaction between NaCl-bearing carbonate melt shifts its composition toward Mg-poor and NaCl-rich. Given the above, an alternative hypothesis can be proposed, according to which the interaction of alkaline chloride-bearing carbonate melts formed in the subduction zones with the reduced mantle should be accompanied by diamond crystallization and shift the composition of the melt from carbonatitic to alkali-rich saline.  相似文献   

Low melting temperature for calcite at 1000 bars on the join CaCO3‐H2O – some geological implications          下载免费PDF全文

Cyril Durand  Lukas P. Baumgartner  Didier Marquer 《地学学报》2015,27(5):364-369

Melting experiments of calcite were performed on the join CaCO₃‐H₂O at a pressure of 1000 bars. The system evolves to the ternary CaO‐H₂O‐CO₂ system during melting experiments. Our experiments show that partial melting of calcite begins at a low temperature, below 650 °C. Such a low partial melting temperature for carbonates revives the debate about the presence of carbonate melts in the upper crust. More specifically, the conditions for carbonate partial melting are present in carbonate host rocks undergoing contact metamorphism at high temperatures in the presence of water‐rich fluid. The presence of carbonate melts influences physical parameters such as viscosity and permeability in contact aureoles, and, furthermore, decarbonation reactions release massive amounts of CO₂.  相似文献   

Experimental investigation of the metamorphism of siliceous dolomites     

Hans -Rolf Käse  Paul Metz 《Contributions to Mineralogy and Petrology》1980,73(2):151-159

For the reaction: 1 diopside+3 dolomite ?2 forsterite+4 calcite+2 CO₂ (14) the following P _total?T-brackets have been determined experimentally in the presence of a gasphase consisting of 90 mole%CO₂ and 10 mole%H₂O∶1 kb, 544°±20° C; 3kb, 638°±15° C; 5kb, 708°±10° C; 10kb, 861°±10° C. The determination was carried out with well defined synthetic minerals in the starting mixture. The MgCO₃-contents of the magnesian calcites formed by the reaction in equilibrium with dolomite agree very well with the calcite-dolomite miscibility gap, which can be recalculated from the activities and the activity coefficients of MgCO₃ as given by Gordon and Greenwood (1970). The equilibrium constant K _14b was calculated with respect to the reference pressure P ₀=1 bar using the experimentally determined \(P_{total} TX_{CO_2 }\) brackets, the activities of MgCO₃ and CaCO₃ (Gordon and Greenwood 1970; Skippen 1974) and the fugacities of CO₂ Holloway (1977) considering the correction of Flowers (1979). Results are plotted as function of the absolute reciprocal temperature in Fig. 1. For the temperature range of 530° to 750° C the following linear expression can be given for the natural logarithm of K_14b: (g) $$[ln K_{14b} ]_T^P = - \frac{{18064.43}}{{T\left( {^\circ K} \right)}} + 38.58 + \frac{{0.308(P - 1 bar)}}{{T\left( {^\circ K} \right)}}$$ where P is the total pressure in bars and T the temperature in degrees Kelvin. Combining Equation (g) with the activities of MgCO₃ and CaCO₃ gives the equilibrium fugacity \(f_{CO_2 }\) : (i) $$[ln f_{CO_2 } ]_T^P = - \frac{{11635.44}}{{T\left( {^\circ K} \right)}} + 21.09 + \frac{{0.154(P - 1 bar)}}{{T\left( {^\circ K} \right)}}$$ Equation (i) and the fugacities of CO₂ permit to calculate the equilibrium data in terms of \(P_{CO_2 }\) and T (see Fig. 3) or P _total, T and \(X_{CO_2 }\) (see Fig. 5). Combining the \(P_{total} TX_{CO_2 }\) equilibrium data of the above reaction with those of the previously investigated reaction (Metz 1976): 1 tremolite+11 dolomite ?8 forsterite+13 calcite+9 CO₂+1 H₂O yields the stability conditions of the four-mineral assemblage: diopside+calcian dolomite+forsterite +magnesian calcite and the stability conditions of the five-mineral assemblage: tremolite+calcian dolomite+forsterite +magnesian calcite+diopside both shown in Fig. 6. Since these assemblages are by no means rare in metamorphic siliceous dolomites (Trommsdorff 1972; Suzuki 1977; Puhan 1979) the data of Fig. 6 can be used to determine the pressure of metamorphism and to estimate the composition of the CO₂-H₂O fluid provided the temperature of the metamorphic event was determined using the calcite-dolomite geothermometer.  相似文献   

The solubilities of calcite,aragonite and vaterite in CO₂-H₂O solutions between 0 and 90°C,and an evaluation of the aqueous model for the system CaCO₃-CO₂-H₂O     

L.Niel Plummer  Eurybiades Busenberg 《Geochimica et cosmochimica acta》1982,46(6):1011-1040

Calculations based on approximately 350 new measurements (Ca_T-PCO₂) of the solubilities of calcite, aragonite and vaterite in CO₂-H₂O solutions between 0 and 90°C indicate the following values for the log of the equilibrium constants K_C, K_A, and K_V respectively, for the reaction CaCO₃(s) = Ca²⁺ + CO^2?₃: $\text{Log K}{}_{\mathrm{C}}\text{= ?171.9065 ? 0.077993T +}\text{2839.319}\text{T}\text{+ 71.595 log T}$$\text{Log K}{}_{\mathrm{A}}\text{= ?171.9773 ? 0.077993T +}\text{2903.293}\text{T}\text{+71.595 log T}$$\text{Log K}{}_{\mathrm{V}}\text{= ?172.1295 ? 0.077993T +}\text{3074.688}\text{T}\text{+ 71.595 log T}$ where T is in ^oK. At 25°C the logarithms of the equilibrium constants are ?8.480 ± 0.020, ?8.336 ± 0.020 and ?7.913 ± 0.020 for calcite, aragonite and vaterite, respectively.The equilibrium constants are internally consistent with an aqueous model that includes the CaHCO⁺₃ and CaCO⁰₃ ion pairs, revised analytical expressions for CO₂-H₂O equilibria, and extended Debye-Hückel individual ion activity coefficients. Using this aqueous model, the equilibrium constant of aragonite shows no PCO₂-dependence if the CaHCO⁺₃ association constant is between 0 and 90°C, corresponding to the value logK_Cahco⁺3 = 1.11 ± 0.07 at 25°C. The CaCO⁰₃ association constant was measured potentiometrically to be between 5 and 80°C, yielding logK_CaCO⁰3 = 3.22 ± 0.14 at 25°C.The CO₂-H₂O equilibria have been critically evaluated and new empirical expressions for the temperature dependence of K_H, K₁ and K₂ are $\text{log K}{}_{\mathrm{H}}\text{= 108.3865 + 0.01985076T ?}\text{6919.53}\text{T}\text{? 40.45154 log T +}\text{669365.}\text{T}{}^2$, $\text{log K}{}_1\text{= ?356.3094 ? 0.06091964T +}\text{21834.37}\text{T}\text{+ 126.8339 log T —}\text{1684915.}\text{T}{}^2$ and logK₂ = ?107.8871 ? 0.03252849T + 5151.79/T + 38.92561 logT ? 563713.9/T² which may be used to at least 250°C. These expressions hold for 1 atm. total pressure between 0 and 100°C and follow the vapor pressure curve of water at higher temperatures.Extensive measurements of the pH of Ca-HCO₃ solutions at 25°C and 0.956 atm PCO₂ using different compositions of the reference electrode filling solution show that measured differences in pH are closely approximated by differences in liquid-junction potential as calculated by the Henderson equation. Liquid-junction corrected pH measurements agree with the calculated pH within 0.003-0.011 pH.Earlier arguments suggesting that the CaHCO⁺₃ ion pair should not be included in the CaCO₃-CO₂-H₂O aqueous model were based on less accurate calcite solubility data. The CaHCO⁺₃ ion pair must be included in the aqueous model to account for the observed PCO₂-dependence of aragonite solubility between 317 ppm CO₂ and 100% CO₂.Previous literature on the solubility of CaCO₃ polymorphs have been critically evaluated using the aqueous model and the results are compared.  相似文献   

Thermochemistry of glasses and liquids in the systems CaMgSi₂O₆-CaAl₂Si₂O₈-NaAlSi₃O₈, SiO₂-CaAl₂Si₂O₈-NaAlSi₃O₈ and SiO₂-Al₂O₃-CaO-Na₂O     

A. Navrotsky  R. Hon  D.F. Weill  D.J. Henry 《Geochimica et cosmochimica acta》1980,44(10):1409-1423

Enthalpies of solution in 2PbO· B₂O₃ at 712°C have been measured for glasses in the systems albite anorthite diopside, NaAlO₂-SiO₂, Ca_0.5AlO₂-SiO₂ and albite-anorthite-quartz. The systems albite-anorthite and diopside-anorthite show substantial negative enthalpies of mixing, albite-diopside shows significant positive heats of mixing. For compositions up to NaAlO₂ = 0.42 (which includes the subsystem albite-silica) the system NaAlO₂-SiO₂ shows essentially zero heats of mixing. A negative ternary excess heat of mixing is found in the plagioclase-rich portion of the albite-anorthite-diopside system. The join Si₄O₈-CaAl₂Si₂O₈ shows small but significant heats of mixing. In albite-anorthite-quartz. ternary glasses, the ternary excess enthalpy of mixing is positive.Based on available heat capacity data and appropriate consideration of the glass transition, the enthalpy of the crystal-glass transition (vitrification) is a serious underestimate of the enthalpy of the crystal-liquid transition (fusion) especially when the melting point, T_f, is many hundreds of degrees higher than the glass transition temperature, T_g. On the other hand, the same heat capacity data suggest that the enthalpies of mixing in albite-anorthite-diopside liquids are calculated to be quite similar to those in the glasses. The enthalpies of mixing observed in general support the structural models proposed by Taylor and Brown (1979a, b) and others for the structure of aluminosilicate glasses.  相似文献   

Thermochemistry of synthetic clinopyroxenes on the join CaMgSi₂O₆-Mg₂Si₂O₆     

R.C. Newton  T.V. Charlu  P.A.M. Anderson  O.J. Kleppa 《Geochimica et cosmochimica acta》1979,43(1):55-60

Enthalpies of solution of synthetic clinopyroxenes on the join CaMgSi₂O₆-Mg₂Si₂O₆ have been measured in a melt of composition Pb₂B₂O₅ at 970 K. Most of the measurements were made on samples crystallized at 1600°–1700°C and 30 kbar pressure, which covered the range 0–78 mole per cent Mg₂Si₂O₆, and whose X-ray patterns could be satisfactorily indexed on the diopside (C2/c) structure. For the reaction: Mg₂Si₂O₆→-Mg₂Si₂O₆ enstatite diopside the present data, in conjunction with previous and new measurements on Mg₂Si₂O₆ enstatite, determine ΔH° ~ 2 kcal and W_H (regular solution parameter) ~ 7 kcal. These values are in good agreement with those deduced by Saxena and Nehru (1975) from a study of high temperature, high pressure phase equilibrium data under the assumption that the excess entropy of mixing is small, but, in light of the recent theoretical treatment of Navrotsky and Loucks (1977, Phys. Chem. Min.1, 109–127), the meanings of these parameters may be ambiguous.Heat of solution measurements on Ca-rich binary diopsides made by annealing glasses at 1358°C in air gave slighter higher values than the higher temperature high pressure samples. This may be evidence for some (Ca, Mg) disorder of the sort postulated by Navrotsky and Loucks (1977, Phys. Chem. Min.1, 109–127), although no differences in heat of solution dependent on synthesis temperature in the range 1350°–1700°C could be found in stoichiometric CaMgSi₂O₆.  相似文献   

Reaction kinetics of dolomite rim growth     

V. Helpa  E. Rybacki  R. Abart  L. F. G. Morales  D. Rhede  P. Jeřábek  G. Dresen 《Contributions to Mineralogy and Petrology》2014,167(4):1-14

Reaction rims of dolomite (CaMg[CO₃]₂) were produced by solid-state reactions at the contacts of oriented calcite (CaCO₃) and magnesite (MgCO₃) single crystals at 400 MPa pressure, 750–850 °C temperature, and 3–146 h annealing time to determine the reaction kinetics. The dolomite reaction rims show two different microstructural domains. Elongated palisades of dolomite grew perpendicular into the MgCO₃ interface with length ranging from about 6 to 41 µm. At the same time, a 5–71 µm wide rim of equiaxed granular dolomite grew at the contact with CaCO₃. Platinum markers showed that the original interface is located at the boundary between the granular and palisade-forming dolomite. In addition to dolomite, a 12–80 µm thick magnesio-calcite layer formed between the dolomite reaction rims and the calcite single crystals. All reaction products show at least an axiotactic crystallographic relationship with respect to calcite reactant, while full topotaxy to calcite prevails within the granular dolomite and magnesio-calcite. Dolomite grains frequently exhibit growth twins characterized by a rotation of 180° around one of the $[11\bar{2}0]$ equivalent axis. From mass balance considerations, it is inferred that the reaction rim of dolomite grew by counter diffusion of MgO and CaO. Assuming an Arrhenius-type temperature dependence, activation energies for diffusion of CaO and MgO are E _a (CaO) = 192 ± 54 kJ/mol and E _a (MgO) = 198 ± 44 kJ/mol, respectively.  相似文献   

Grain growth kinetics of dolomite,magnesite and calcite: a comparative study     

N. E. Davis  J. Newman  P. B. Wheelock  A. K. Kronenberg 《Physics and Chemistry of Minerals》2011,38(2):123-138

The rates of grain growth of stoichiometric dolomite [CaMg(CO₃)₂] and magnesite (MgCO₃) have been measured at temperatures T of 700–800°C at a confining pressure P _c of 300 MPa, and compared with growth rates of calcite (CaCO₃). Dry, fine-grained aggregates of the three carbonates were synthesized from high purity powders by hot isostatic pressing (HIP); initial mean grain sizes of HIP-synthesized carbonates were 1.4, 1.1, and 17 μm, respectively, for CaMg(CO₃)₂, MgCO₃, and CaCO₃, with porosities of 2, 28, and 0.04% by volume. Grain sizes of all carbonates coarsened during subsequent isostatic annealing, with mean values reaching 3.9, 5.1, and 27 μm for CaMg(CO₃)₂, MgCO₃, and CaCO₃, respectively, in 1 week. Grain growth of dolomite is much slower than the growth rates of magnesite or calcite; assuming normal grain growth and n = 3 for all three carbonates, the rate constant K for dolomite (≃5 × 10⁻⁵ μm³/s) at T = 800°C is less than that for magnesite by a factor of ~30 and less than that for calcite by three orders of magnitude. Variations in carbonate grain growth may be affected by differences in cation composition and densities of pores at grain boundaries that decrease grain boundary mobility. However, rates of coarsening correlate best with the extent of solid solution; K is the largest for calcite with extensive Mg substitution for Ca, while K is the smallest for dolomite with negligible solid solution. Secondary phases may nucleate at advancing dolomite grain boundaries, with implications for deformation processes, rheology, and reaction kinetics of carbonates.  相似文献   

Thermochemistry of high pressure garnets and clinopyroxenes in the system CaO-MgO-Al₂O₃-SiO₂     

R.C. Newton  T.V. Charlu  O.J. Kleppa 《Geochimica et cosmochimica acta》1977,41(3):369-377

The enthalpies of solution of several synthetic garnets on the join Mg₃Al₂Si₃O₁₂-Ca₃Al₂Si₃O₁₂ (pyrope-grossular) and of several synthetic clinopyroxenes on the join CaMgSi₂O₆-CaAl₂SiO₆ (diopside-Ca-Tschermak's molecule) were measured in a melt of composition 2PbO · B₂O₃ at 970 K. The determinations were made with sufficient precision so that thermochemical characterizations of the solid solutions could be achieved.The pyrope-grossular solutions show positive enthalpies of mixing. The non-ideality in the range 0–30 mole % grossular is relatively the largest and is in good agreement with the predictions of Ganguly and Kennedy (1974) based largely on cation partitioning of natural high grade metamorphic garnets with biotite, and with the deductions of Hensenet al. (1975) based on measurement of the compositions of synthetic pyrope-rich garnets equilibrated with anorthite, Al₂SiO₅ and quartz. However, the garnets show smaller excess enthalpies at higher grossular contents. This would lead to an asymmetric solvus with a critical temperature lower than predicted by the symmetrical regular solution model of Ganguly and Kennedy (1974). The composition-dependent non-ideality can be understood by simple ionic size considerations in solid substitution and is analogous to the situations for the calcite-dolomite and enstatite-diopside solvi.The heats of solution of pyropes crystallized in the range 1000–1500°C were all the same, within the precision of measurement, and thus we have found no evidence for temperature-dependent cation disordering as a possible explanation of the high entropy of pyrope, as suggested by Charluet al. (1975). Positional disorder of dodecahedral Mg is a more probable reason.The diopside-CaTs join is also non-ideal, with the larger positive enthalpy deviations near the diopside end. The calorimetric data in the magnesian range are consistemt with the model for completely disordered tetrahedral Si and Al which results from the free energy derivations of wood (1975) based on syntheses of diopside-rich aluminous pyroxenes in the presence of anorthite and quartz. At higher Al concentrations the calorimetric data seem more consistent with the ‘local charge-balance’ model of Wood (1975).No evidence for temperature-dependent disorder was found for either the diopside or CaTs end-members.  相似文献   

Peridotite–eclogite–carbonatite systems at 7.0–8.5 GPa: concentration barrier of diamond nucleation and syngenesis of its silicate and carbonate inclusions     

A.V. Bobrov  Yu.A. Litvin 《Russian Geology and Geophysics》2009,50(12):1221-1233

Diamond crystallization in multicomponent melts of variable composition is studied. The melt carbonates are K₂CO₃, CaCO₃?MgCO₃, and K-Na-Ca-Mg-Fe-carbonatites, and the melt silicates are model peridotite (60 wt.% olivine, 16 wt.% orthopyroxene, 12 wt.% clinopyroxene, and 12 wt.% garnet) and eclogite (50 wt.% garnet and 50 wt.% clinopyroxene). In the experiments carried out under the PT-conditions of diamond stability, the carbonate-silicate melts behave like completely miscible liquid phases. The concentration barriers of diamond nucleation (CBDN) in the melts with variable proportions of silicates and carbonates have been determined at 8.5 GPa. In the system peridotite–K₂CO₃–CaCO₃?MgCO₃–carbonatite they correspond to 30, 25, and 30 wt.% silicates, respectively, and in the analogous eclogite–carbonate system, 45, 30, and 35 wt.%. In the silicate-carbonate melts with higher silicate contents seed diamond growth occurs, which is accompanied by the crystallization of thermodynamically unstable graphite phase. In the experiments with melts compositionally corresponding to the CBDN at 7.0 GPa and 1200–1700 °C, a full set of silicate minerals of peridotite (olivine, orthopyroxene, clinopyroxene, garnet) and eclogite (garnet, clinopyroxene) parageneses was obtained. The minerals occur as syngenetic inclusions in natural diamonds; moreover, the garnets contain an impurity of Na, and the pyroxenes, K. The experimental data indicate that peridotite-carbonate and eclogite-carbonate melts are highly effective for the formation of diamond (or unstable graphite) together with syngenetic minerals and melts, which agrees with the carbonate-silicate (carbonatite) model for the mantle diamond formation.  相似文献   

Complex formation in the ternary system Mg(II)-CO₂-H₂O     

Walter Riesen  Heinz Gamsjäger  Paul W. Schindler 《Geochimica et cosmochimica acta》1977,41(9):1193-1200

The carbonato and hydrogencarbonato complexes of Mg²⁺ were investigated at 25 and 50° in solutions of the constant ClO₄^? molality (3 M) consisting preponderantly of NaClO₄. The experimental data could be explained assuming the following equilibria: Mg²⁺ + CO_2B + H₂O ag MgHCO⁺₃ + H⁺, $\text{log}{}^1\text{β}{}_1\text{= ?7.64}{}_4\text{± 0.01}{}_7\text{(25°), ?7.46}{}_2\text{± 0.01}{}_1\text{(50°)}$, Mg²⁺ + 2 CO_2g + 2 H₂Oag Mg(HCO₃)⁰₂ ± 2 H⁺, $\text{log}{}^1\text{β}{}_2\text{= ?15.00 ± 0.14 (25°)}$, ?15.37 ± 0.39 (50°), Mg²⁺ + CO_2g + H₂Oag MgCO⁰₃ + 2 H⁺, $\text{log}{}^1\text{k}{}_1\text{= ?15.64 ± 0.06 (25°)}$,?15.23 ± 0.02 (50°), with the assumption γ_MgCO3⁰ = γ_Mg(HCO3)⁰2, ΔG⁰(I = 0) for the reaction MgCO⁰₃ + CO_2g + H₂O = Mg(HCO₃)⁰₂ was estimated to be ?3.9₁ ± 0.8₆ and 0.6 ± 2.4 kJ/mol at 25 and 50°C, respectively. The abundance of carbonate linked Mg(II) species in fresh water systems is discussed.  相似文献   

Low-temperature thermodynamic model for the system Na2CO3−MgCO3−CaCO3−H2O     

《Geochimica et cosmochimica acta》1999,63(19-20):3105-3119

A comprehensive low-temperature thermodynamic model for the geochemically important Na₂CO₃−MgCO₃−CaCO₃−H₂O system is presented. The model is based on calorimetrically determined Δ_fH°₂₉₈ values, S°₂₉₈ values and C°_p(T) functions taken from the literature as well as on μ°₂₉₈ values of solids derived in this work from solubility measurements obtained in our laboratories or by others. When these thermodynamic quantities were combined with temperature-dependent Pitzer parameters taken from the literature, solubilities calculated for a wide range of conditions agree well with experimental data. The results for several subsystems were summarized by depicting the respective phase diagrams. For the MgO−CO₂−H₂O subsystem, it was found that the commonly believed stability relations must be revised, i.e., in the temperature range covered, nesquehonite never becomes more stable than hydromagnesite at p_CO2 ≤ 1 atm. Although the recommended set of thermodynamic data on sparingly soluble solids was derived from experimental results on mainly NaClO₄ systems, it can be incorporated in databanks containing additional Pitzer parameters for modeling more complex fresh- or seawater systems.  相似文献   

Calculation of subsolidus phase relations in carbonates and pyroxenes     

Alexandra Navrotsky  Douglas Loucks 《Physics and Chemistry of Minerals》1977,1(1):109-127

This formulation of the free energy of mixing in a binary system takes as parameters a Bragg-Williams type cooperative disordering energy and the difference in free energy between different structures for the end-members. Subsolidus phase relations in carbonate systems such as CaCO₃—MgCO₃ and CdCO₃—MgCO₃ are calculated. Similar equations also reproduce the topologies of subsolidus phase relations in pyroxenes, including orthopyroxene-clinopyroxene phase boundaries in the enstatitediopside and ferrosilite-hedenbergite systems, the pigeonite-augite solvus, and the stability field of iron-free pigeonite.  相似文献