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1.
Abstract This, the first two papers, sets out the philosophy and methods of determining an internally consistent thermodynamic dataset for minerals using the least squares method. The applicability of the least squares method is discussed, and it is applied to a small set of experimental equilibria in the system Na2O–Al2O3–SiO2–H2O. The importance is stressed of defining not only the enthalpies of formation of minerals, but also the uncertainties and the correlations among them. The system which has been used as an illustration for this paper serves as a visual guide to the method, as it is small enough to represent graphically in two dimensions. In the paper which follows, we extend the method to a system of 60 equations (experimentally determined equilibria) involving 34 unknowns (enthalpies of formation of mineral end-members).  相似文献   

2.
A recent thermodynamic model for the Na–Ca clinoamphiboles in the system Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–O (NCFMASHO), is improved, and extended to include cummingtonite–grunerite and the orthoamphiboles, anthophyllite and gedrite. The clinoamphibole model in NCMASH is adopted, but the extension into the FeO- and Fe2O3-bearing systems is revised to provide thermodynamic consistency and better agreement with natural assemblage data. The new model involves order–disorder of Fe–Mg between the M2, M13 and M4 sites in the amphibole structure, calibrated using the experimental data on site distributions in cummingtonite–grunerite. In the independent set of end-members used to represent the thermodynamics, grunerite (rather than ferroactinolite) is used for FeO, with two ordered Fe–Mg end-members, and magnesioriebeckite (rather than ferritschermakite) is used for Fe2O3. Natural assemblage data for coexisting clinoamphiboles are used to constrain the interaction energies between the various amphibole end-members. For orthamphibole, the assumption is made that the site distributions and the non-ideal formulation is the same as for clinoamphibole. The data set end-members anthophyllite, ferroanthophyllite and gedrite, are used; for the others, they are based on the clinoamphibole end-members, with the necessary adjustments to their enthalpies constrained by natural assemblage data for coexisting clino- and orthoamphiboles. The efficacy of the models is illustrated with P – T grids and various pseudosections, with a particular emphasis on the prediction of mineral assemblages in ferric-bearing systems.  相似文献   

3.
A thermodynamic model for titanium and ferric iron solution in biotite   总被引：6，自引：1，他引：5  
Recent crystallographic data indicate that in biotite Ti orders preferentially onto the M2 octahedral site rather than onto the M1 site as assumed in previous solution models for K2O–FeO–MgO–Al2O3–SiO2–H2O–TiO2–O2 (KFMASHTO) biotite. In view of these data, we reformulate and reparameterize former biotite solution models. Our reparameterization takes into account Fe–Mg order–disorder and ferric iron contents of natural biotite as well as both natural and experimental observations on biotite Ti-content over a wide range of physicochemical conditions. In comparison with previous biotite models, the new model reproduces the Ti-content and stability field of biotite as constrained by experiments with significantly better accuracy. The predictive power of the model is tested by comparison with petrologically well-characterized natural samples of SiO2-saturated and SiO2-undersaturated rocks that were not used in the parameterization. In all these tests, the reformulated model performs well.  相似文献   

4.
A new petrogenetic grid is presented for the system NCKFMASH (Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–H2O), in which Ca is incorporated in garnet, and CaAlNa−1Si−1 solid solution is considered for both the plagioclase and white-mica structures. A compatibility diagram for plagioclase-bearing metapelitic assemblages within the NCKFMASH system also has been derived. A dominant feature of the NCKFMASH grid is the singularities and associated singular reactions which occur along plagioclase+margarite- and plagioclase+paragonite-bearing univariant equilibria. The singularities represent compositional coplanarities which occur in response to the CaAlNa−1Si−1 substitution occurring at different rates in plagioclase and white-mica. This is controlled by a fundamental difference in the mixing within the two mineral structures. The singularities give rise to a number of intriguing phase diagram features, including azeotropes. From the results presented here, it is predicted that the occurrence of margarite and paragonite in pelitic rocks is controlled by equilibria related to the singularities. The presence of these white-micas is strongly dependent upon bulk composition, and plagioclase-bearing, margarite/paragonite-free assemblages, typical of Barrovian-type terranes, are predicted for bulk compositions of Mg/(Mg+Fe)≈0.4 and Ca/(Ca+Na)≈0.4 at for example 5.5  kbar.  相似文献   

5.
Abstract An experimental study of the system CaCO3–MgCO3–FeCO3 was undertaken in order to calibrate the iron correction to the calcite–dolomite geothermometer, which is based on the solubility of magnesium in calcite in the assemblage calcite + dolomite. The experiments, at 450°C and lower temperatures, resulted in products with a very small grain size and incomplete equilibration. However, application of a carefully-devised automatic data processing algorithm to analyses of the phases in experimental charges, combined with a thermodynamic analysis, results in geothermometer diagrams which should be preferred to previous theoretical predictions.  相似文献   

6.
The high- P , medium- T  Pouébo terrane of the Pam Peninsula, northern New Caledonia includes barroisite- and glaucophane-bearing eclogite and variably rehydrated equivalents. The metamorphic evolution of the Pouébo terrane is inferred from calculated P–T  and P–T  – X H2O pseudosections for bulk compositions appropriate to these rocks in the model system CaO–Na2O–FeO–MgO–Al2O3–SiO2–H2O. The eclogites experienced a clockwise P–T  path that reached P ≈19  kbar and T  ≈600  °C. The eclogitic mineral assemblages are preserved because reaction consequent upon decompression consumed the rocks' fluid. Extensive reaction occurred only in rocks with fluid influx during decompression of the Pouébo terrane.  相似文献   

7.
The equilibrium constant, K a, of the association reaction to form ion pairs from charged solute species in supercritical solutions can be calculated from a model based on published equations. Log K a at constant pressure is a linear function of the inverse in the dielectric constant of the fluid times temperature. The dielectric properties of H2O and CO2 at supercritical pressures and temperatures can also be evaluated using the Kirkwood equation. Using Looyenga mixing rules, the dielectric constant of H2O–CO2 mixtures can be obtained and the change in log K a with addition of CO2 in aqueous solutions evaluated. These changes in log K a with addition of CO2 are consistent with measured changes of log K a with addition of Ar in supercritical H2O–Ar solutions.
Log K a of KCl and NaCl increase to an increasing extent as the mole fraction of CO2 increases in H2O–CO2 solutions. For instance, at 2 kbar and constant temperature between 400 and 600° C, log K a of KCl increases by about two orders of magnitude whilst that of NaCl increases by over four orders of magnitude as the CO2 mole fraction increases from 0.0 to 0.35. Such changes in log K a will have dramatic effects on the solubility of minerals in CO2-rich environments.  相似文献   

8.
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9.
Hydration of eclogite, Pam Peninsula, New Caledonia   总被引：2，自引：0，他引：2  
Garnet glaucophanite and greenschist facies assemblages were formed by the recrystallization of barroisite-bearing eclogite facies metabasites in northern New Caledonia. The mineralogical evolution can be modelled by calculated P–T and P–X H2O diagrams for appropriate bulk rock compositions in the model system CaO–Na2O–FeO–MgO–Al2O3–SiO2–H2O. The eclogites, having developed in a clockwise P–T path that reached P ≈19 kbar and T  ≈590 °C, underwent decompression with the consumption of free H2O as the volume of hydrous minerals increased. Eclogite is preserved in domains that experienced no fluid influx following the loss of this fluid. Garnet glaucophanite formed at P ≈16 kbar during semi-pervasive fluid influx. Fluid influx, after further isothermal decompression, was focused in shear zones, and resulted in chlorite–albite-bearing greenschist facies mineral assemblages that reflect P ≈9 kbar.  相似文献   

10.
The internal energies and entropies of 21 well-known minerals were calculated using the density functional theory (DFT), viz. kyanite, sillimanite, andalusite, albite, microcline, forsterite, fayalite, diopside, jadeite, hedenbergite, pyrope, grossular, talc, pyrophyllite, phlogopite, annite, muscovite, brucite, portlandite, tremolite, and CaTiO3–perovskite. These thermodynamic quantities were then transformed into standard enthalpies of formation from the elements and standard entropies enabling a direct comparison with tabulated values. The deviations from reference enthalpy and entropy values are in the order of several kJ/mol and several J/mol/K, respectively, from which the former is more relevant. In the case of phase transitions, the DFT-computed thermodynamic data of involved phases turned out to be accurate and using them in phase diagram calculations yields reasonable results. This is shown for the Al2SiO5 polymorphs. The DFT-based phase boundaries are comparable to those derived from internally consistent thermodynamic data sets. They even suggest an improvement, because they agree with petrological observations concerning the coexistence of kyanite?+?quartz?+?corundum in high-grade metamorphic rocks, which are not reproduced correctly using internally consistent data sets. The DFT-derived thermodynamic data are also accurate enough for computing the P–T positions of reactions that are characterized by relatively large reaction enthalpies (>?100 kJ/mol), i.e., dehydration reactions. For reactions with small reaction enthalpies (a few kJ/mol), the DFT errors are too large. They, however, are still far better than enthalpy and entropy values obtained from estimation methods.  相似文献   

11.
A petrogenetic grid is presented for the system KFMASH (K2O-FeO-MgO-Al2O3-SiO2-H2O), including biotite, muscovite, K-feldspar, chlorite, chloritoid, staurolite, cordierite, garnet, orthoamphibole, orthopyroxene, spinel, andalusite, sillimanite, kyanite, quartz and corundum with H2O in excess, which was calculated using the computer program THERMOCALC and the Powell and Holland internally consistent thermodynamic dataset. By removing the normal constraint of having quartz in excess, both quartz-bearing and quartz-absent equilibria are shown. Quartz-absent equilibria are particularly relevant at high- T and low- P conditions, because of their common occurrence at these conditions. The calculated mineral assemblage and mineral compositional variations in terms of FeMg-1 and (Fe, Mg)SiAl-2 exchange vectors are broadly compatible with observations on natural rocks, particularly when non-KFMASH components are taken into account.  相似文献   

12.
The solid-solid reaction magnesiocarpholite = sudoite + quartz has been bracketed between 350 and 500°C, 6.3 and 7.8 kbar. Because it is impossible to synthesize end-member sudoite, all experiments were carried out using natural minerals as starting materials. Although mineral compositions were very close to those of the end-members, the effect of the fluorine content in carpholite was significant. Particularly in those experiments where sudoite grows at the expense of carpholite, electron microprobe analysis of the run products shows that a more stable F-rich carpholite crystallizes too, and consumes the fluorine released in solution by the breakdown of the original carpholite.
Our experimental results are combined, through a thermodynamic analysis, with a previous data set and with previous experimental data concerning the relative stability of chlorite, talc and magnesiocarpholite with excess of quartz and water as a function of P–T and AlAl(SiMg)-1 substitutions in phyllosilicates. This allows us to constrain the feasible thermodynamic parameters (H°f, sud; S ° sud) and (H°f,car; S °car) for the Mg end-members. Using the partition coefficients calculated from natural parageneses, we have computed a petrogenetic grid for the system FeO–MgO–Al2O3–SiO2–H2O. It demonstrates that parageneses involving sudoite and carpholite can be used as indicators of P–T conditions, up to 600° C, 8 kbar for sudoite, and at higher pressure for carpholite.  相似文献   

13.
Calcsilicate granulites of probable Middle Proterozoic age ( c .1000–1100  Ma) in the vicinity of Battye Glacier, northern Prince Charles Mountains, East Antarctica, contain prograde metamorphic assemblages comprising various combinations of wollastonite, scapolite, clinopyroxene, An-rich plagioclase, calcite, quartz, titanite and, rarely, orthoclase, ilmenite, phlogopite and graphite. Comparison of the prograde assemblages with calculated and experimentally determined phase relations in the simple CaO–Al2O3–SiO2–CO2–H2O system suggests peak metamorphism at ≥835 °C in the presence (in wollastonite-bearing assemblages at least) of a CO2-bearing fluid ( X CO≥0.3) at a probable pressure of 6–7  kbar.
Well-preserved retrograde reaction textures represent: (1) breakdown of scapolite to anorthite+calcite±quartz; (2) formation of grossular–andradite garnet and, locally, (3) epidote, both principally by reactions involving scapolite breakdown products and clinopyroxene; (4) local coupled replacement of clinopyroxene and ilmenite by hornblende and titanite, respectively; and finally (5) local sericitization of prograde and retrograde plagioclase. These retrograde reactions are interpreted to be the result of cooling and variable infiltration by H2O-rich fluids, possibly derived from crystallizing pegmatitic intrusions and segregations that may be partial melts, which are common throughout the area.  相似文献   

14.
The cathodoluminescence analyses of the trigonal carbonates calcite and dolomite have been applied intensively in sedimentary petrology for a long time and the properties of these minerals are well-known, but much less attention has been paid to aragonite. In this study, the cathodoluminescence behaviour and the trace element composition of natural and synthetic aragonite have been studied employing trace element analyses (proton induced X-ray emission) and luminescence spectroscopy. Aragonite doped with Mn2+ has been synthesized in a NH4+–Mg2+–Ca2+–Cl− solution in contact with a CO2–H2O–NH3 atmosphere. The low effective distribution coefficients indicate a rapid growth of the crystals of millimetre size which occurred within hours or days. The natural aragonite samples contain Mn, Fe and Sr in different concentrations. The Mn-bearing aragonites exhibit a bright green luminescence which is caused by a strong emission band at 575 nm with a half-width of about 84 nm. The luminescence intensity shows a strong positive correlation with Mn in aragonite when Fe and Mn do not exceed 2000 p.p.m. The intensity is depressed if the concentration of these elements exceeds the critical values. In the shell of a recent Unio sp., the luminescence intensity deviates from the linear correlation, although the trace element contents are not too high; this is probably an effect of quenching by organic material between the crystallites of the biogenic aragonite.  相似文献   

15.
We present, as a progress report, a revised and much enlarged version of the thermodynamic dataset given earlier (Holland & Powell, 1985). This new set includes data for 123 mineral and fluid end-members made consistent with over 200 P–T–XCO2–fO2 phase equilibrium experiments. Several improvements and advances have been made, in addition to the increased coverage of mineral phases: the data are now presented in three groups ranked according to reliability; a large number of iron-bearing phases has been included through experimental and, in some cases, natural Fe:Mg partitioning data; H2O and CO2 contents of cordierites are accounted for with the solution model of Kurepin (1985); simple Landau theory is used to model lambda anomalies in heat capacity and the Al/Si order–disorder behaviour in some silicates, and Tschermak-substituted end-members have been derived for iron and magnesium end-members of chlorite, talc, muscovite, biotite, pyroxene and amphibole. For the subset of data which overlap those of Berman (1988), it is encouraging to find both (1) very substantial agreement between the two sets of thermodynamic data and (2) that the two sets reproduce the phase equilibrium experimental brackets to a very similar degree of accuracy. The main differences in the two datasets involve size (123 as compared to 67 end-members), the methods used in data reduction (least squares as compared to linear programming), and the provision for estimation of uncertainties with this dataset. For calculations on mineral assemblages in rocks, we aim to maximize the information available from the dataset, by combining the equilibria from all the reactions which can be written between the end-members in the minerals. For phase diagram calculations, we calculate the compositions of complex solid solutions (together with P and T) involved in invariant, univariant and divariant assemblages. Moreover we strongly believe in attempting to assess the probable uncertainties in calculated equilibria and hence provide a framework for performing simple error propagation in all calculations in thermocalc, the computer program we offer for an effective use of the dataset and the calculation methods we advocate.  相似文献   

16.
The technique of linear parametric programming has been applied to derive sets of internally consistent thermodynamic data for 21 condensed phases of the quaternary system CaO-Al2O3-SiO2-H2O (CASH) (Table 4). This was achieved by simultaneously processing:
  1. calorimetric data for 16 of these phases (Table 1), and
  2. experimental phase equilibria reversal brackets for 27 reactions (Table 3) involving these phases.
Calculation of equilibrium P-T curves of several arbitrarily picked reactions employing the preferred set of internally consistent thermodynamic data from Table 4 shows that the input brackets are invariably satisfied by the calculations (Fig. 2a). By contrast, the same equilibria calculated on the basis of a set of thermodynamic data derived by applying statistical methods to a large body of comparable input data (Haas et al. 1981; Hemingway et al. 1982) do not necessarily agree with the experimental reversal brackets. Prediction of some experimentally investigated phase relations not included into the linear programming input database also appears to be remarkably successful. Indications are, therefore, that the thermodynamic data listed in Table 4 may be used with confidence to predict geologic phase relations in the CASH system with considerable accuracy. For such calculated phase diagrams and their petrological implications, the reader's attention is drawn to the paper by Chatterjee et al. (1984).  相似文献   

17.
Abstract Peridotite and infolded marble of the Seiad ultramafic complex were recrystallized in the upper amphibolite facies as part of the regional progressive metamorphism of the Rattlesnake Creek terrane. Field relations, including the occurrence of metarodingites, and metasomatic zones between dissimilar rock types, demonstrate that the metasediments and serpentinized ultramafic rocks were juxtaposed prior to regional, barrovian metamorphism. Temperatures are estimated to have reached 760–800°C at pressures of 7–8 kbar during the peak of metamorphism. Four low-variance parageneses have been identified within a small (3 km2) area of the complex, which may reasonably be assumed to have formed under the same P and T conditions. Isobaric T-X co2 diagrams of appropriate equilibria are presented for three different internally consistent sets of thermodynamic data. Despite the seemingly small numerical differences between the standard state thermodynamic properties of the data sets, only one diagram allows the four observed assemblages to coexist within a reasonable temperature range. All three phase diagrams require differences in fluid composition on the scale of a thin section; strong evidence for effective control of pore fluid composition by local mineral reactions during metamorphism.  相似文献   

18.
Abstract Petrological data from intercalated pelitic schists and greenstones are used to construct a pressure–temperature path followed by the Upper Schieferhülle (USH) series during progressive metamorphism and uplift in the south-west Tauern Window, Italy. Pseudomorphs of Al–epidote + Fe-epidote + albite + oligoclase + chlorite after lawsonite and data on amphibole crystal chemistry indicate early metamorphism in the lawsonite-albite-chlorite subfacies of the blueschist facies at P ± 7–8 kbar. Geothermometry and geobarometry yield conditions of final equilibration of the matrix assemblage of 475±25°C, 5–6 kbar; calculations with plagioclase and phengite inclusions in garnet indicate early garnet growth at pressures of ∼ 7.5 kbar. Garnet zoning patterns are complex and reversals in zoning can be correlated between samples. Thermodynamic modelling of these zoning profiles implies garnet growth in response to four distinct phases of tectonic activity. Fluid inclusion data from coexisting immiscible H2O–CO2–NaCl fluids constrain the uplift path to have passed through temperatures of 380 + 30°C at 1.3 + 0.2 kbar.
There is no evidence for metamorphism of USH at pressures greater than ∼ 7.5 kbar in this area of the Tauern Window. This is in contrast to pressures of ± 10 kbar recorded in the Lower Schieferhülle only 2–3 km across strike. A history of differential uplift and thinning of the intervening section during metamorphism is necessary to reconcile the P–T data obtained from these adjacent tectonic units.  相似文献   

19.
Abstract Corona textures, which developed in alternating layers in rocks in a supracrustal belt at Errabiddy, Western Australia, involved:
(a) The production of staurolite, cordierite and quartz or sapphirine between Kyanite and/or sillimanite and gedrite; and
(b) The production of cordierite between garnet and gedrite.
These textures are inconsistent with development along the same pressure–temperature path in the system FeO–MgO–Al2O3–SiO2–H2O, but can be accounted for if CaO, mainly in garnet, is taken into account. The sapphirine-bearing kyanite–gedrite textures are explained by lower a (SiO2) during their development. The assemblages indicate a consistent pressure–temperature ( P–T ) trajectory involving substantial uplift with only a slight decrease in temperature. The history of these rocks includes reheating of originally high-grade rocks that had cooled to a stable conductive geotherm, followed by substantial, essentially isothermal uplift. The tectonic environment for this was presumably the one responsible for emplacement of the high-grade terrain in the upper crust.  相似文献   

20.
The thermodynamic properties of 254 end‐members, including 210 mineral end‐members, 18 silicate liquid end‐members and 26 aqueous fluid species are presented in a revised and updated internally consistent thermodynamic data set. The PVT properties of the data set phases are now based on a modified Tait equation of state (EOS) for the solids and the Pitzer & Sterner (1995) equation for gaseous components. Thermal expansion and compressibility are linked within the modified Tait EOS (TEOS) by a thermal pressure formulation using an Einstein temperature to model the temperature dependence of both the thermal expansion and bulk modulus in a consistent way. The new EOS has led to improved fitting of the phase equilibrium experiments. Many new end‐members have been added, including several deep mantle phases and, for the first time, sulphur‐bearing minerals. Silicate liquid end‐members are in good agreement with both phase equilibrium experiments and measured heat of melting. The new dataset considerably enhances the capabilities for thermodynamic calculation on rocks, melts and aqueous fluids under crustal to deep mantle conditions. Implementations are already available in thermocalc to take advantage of the new data set and its methodologies, as illustrated by example calculations on sapphirine‐bearing equilibria, sulphur‐bearing equilibria and calculations to 300 kbar and 2000 °C to extend to lower mantle conditions.  相似文献   

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