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1.
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   

2.
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   

3.
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   

4.
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   

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 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   

7.
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   

8.
A calibration is presented for an activity–composition model for amphiboles in the system Na2O–CaO–FeO–MgO–Al2O3–SiO2–H2O–O (NCFMASHO), formulated in terms of an independent set of six end‐members: tremolite, tschermakite, pargasite, glaucophane, ferroactinolite and ferritschermakite. The model uses mixing‐on‐sites for the ideal‐mixing activities, and for the activity coefficients, a macroscopic multicomponent van Laar model. This formulation involves 15 pairwise interaction energies and six asymmetry parameters. Calibration of the model is based on the geometrical constraints imposed by the size and shape of amphibole solvi inherent in a data set of 71 coexisting amphibole pairs from rocks, formed over 400–600 °C and 2–18 kbar. The model parameters are calibrated by combining these geometric constraints with qualitative consideration of parameter relationships, given that the data are insufficient to allow all the model parameters to be determined from a regression of the data. Use of coexisting amphiboles means that amphibole activity–composition relationships are calibrated independently of the thermodynamic properties of the end‐members. For practical applications, in geothermobarometry and the calculation of phase diagrams, the amphibole activity–composition relationships are placed in the context of the stability of other minerals by evaluating the properties of the end‐members in the independent set that are in internally consistent data sets. This has been performed using an extended natural data set for hornblende–garnet–plagioclase–quartz, giving the small adjustments necessary to the enthalpies of formation of tschermakite, pargasite and glaucophane for working with the Holland and Powell data set.  相似文献   

9.
A ternary solid solution model for omphacite with the end-members jadeite (NaAlSi2O6), diopside (CaMgSi2O6) and hedenbergite (CaFeSi2O6) was derived from experimental data from the literature. The subregular solution model, fitted by linear programming, is best suited to omphacites with very little aegirine component in common eclogites. Applying this solution model to the calculation of equilibrium phase diagrams of eclogites from the Adula nappe (Central Alps, Switzerland) results in large stability fields for common eclogite assemblages (garnet+omphacite+quartz+H2O±kyanite). Within this field the compositions of garnet and omphacite show very little variation. A precise determination of the peak-pressure and temperature is not possible. The occurrence of amphibole, overgrowing the peak-pressure assemblage in fresh eclogite, suggests retrograde re-equilibration, still under eclogite facies conditions. The computation of isopleths for garnet and pyroxene end-members allows the estimation of the pressure and temperature conditions of this re-equilibration event (19–21  kbar, c .  700 °C).  相似文献   

10.
Abstract This, the second of two papers, represents the application of a least squares approach, discussed in the previous paper, to the generation of an internally consistent thermodynamic dataset involving 60 reactions among 43 phases, in the system K2O–Na2O–CaO–MgO–Al2O3–SiO2–H2O–CO2. We make the assumption that all the thermodynamic data, with the exception of enthalpies of formation of the phases, are well known, and solve for an internally consistent set of enthalpies which reproduces the 60, experimentally determined, phase equilibrium reactions. An important difference between our dataset and that of previous alternatives in the literature is that we are able to determine the uncertainties on, and correlations between, the enthalpies of formation for all phases in the set, and hence are able to apply simple error propagation techniques to determine the uncertainties in any phase equilibrium calculations performed using this dataset. Selection of reactions, for geothermometry and geobarometry, may be more readily made by choosing equilibria with small uncertainties in their thermodynamics. Our data are in reasonably close agreement with the high temperature molten oxide calorimetry results on silicate minerals where available, a fact which lends a degree of confidence to the results.  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.
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   

13.
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   

14.
The proposed geothermobarometer is based on an empirical calibration which takes account of two equilibria involving the tremolite, edenite, pargasite and hastingsite components in amphiboles. It has applications to assemblages found in metabasic rocks of widely different chemical compositions (magnesian to Fe-rich metabasalts), and for metamorphism ranging from lower greenschist to highest amphibolite facies. Knowing the Si(T1), Aliv, Alvi, Fe3+, Fe2+, Mg, Ca, NaM4, NaA and A vacancy in an amphibole, and the Al3+ and X Mg in coexisting epidote and chlorite, it is possible to calculate two values of In K d for this assemblage. These equilibria involve edenite-tremolite and (pargasite/hastingsite)-tremolite end-members in amphibole (the calculation program is given). For these equilibria, the isopleths (iso-values of K d) have been calculated for 0.27 < X Mg < 0.75 and 0 < X Fe3+= Fe3+/(Fe3++ Alvi) < 0.8. It is then possible to determine pressure and temperature directly when X Mg, X Fe3+, In K d for tremoliteedenite and In K d for (pargasite/hastingsite)-tremolite are known. Application of this geothermobarometer is limited to Ca-free plagioclase assemblages, and complete P–T paths can be drawn only if all the minerals are considered together. Phase relations at successive stages of crystallization can be constrained by studying the relationships between the coexisting minerals, their zoning and the metamorphic fabrics.  相似文献   

15.
Abstract The Rockley Volcanics from near Oberon, New South Wales occur within the aureole of the Carboniferous Bathurst Batholith and have been contact metamorphosed at P ∼ 100 ± 50MPa (10.5kbar) and a maximum T ∼ 565°C in the presence of a C–O–H fluid. Prior to contact metamorphism the volcanics were regionally metamorphosed and altered with the extensive development of actinolite, chlorite, plagioclase, quartz and calcite. The contact metamorphosed equivalents of these rocks have been subdivided into: Ca-poor (cordierite + gedrite), Mg-rich (amphibole + olivine + spinel), mafic (amphibole + plagioclase) and Ca-rich (amphibole + garnet + diopside; diopside + plagioclase; garnet + diopside + wollastonite) rocks.
The chemistry of the minerals in the hornfelses was controlled by the bulk rock chemistry and fluid composition. Pargasites and hastingsites as well as an unusual phlogopite with blue green pleochroism, are found in Ca-rich hornfelses. A comparison of the assemblages with experimentally derived equilibria suggests that the fluid phase associated with the Ca-rich hornfelses was water-rich (Xco2= 0.1 to 0.3) while that associated with the Mg-rich hornfelses was enriched in CO2 (Xco2 > 0.7). The different hornfels types have reacted to contact metamorphism independently in both their solid and fluid chemistries.  相似文献   

16.
Silica-deficient sapphirine-bearing rocks occur as an enclave within granulite facies Proterozoic gneisses and migmatites near Grimstad in the Bamble sector of south-east Norway (Hasleholmen locality). The rocks contain peraluminous sapphirine, orthopyroxene, gedrite, anthophyllite, sillimanite, sapphirine, corundum, cordierite, spinel, quartz and biotite in a variety of assemblages. Feldspar is absent.
Fe2+/(Fe2++ Mg) in the analysed minerals varies in the order: spinel > gedrite ≥ anthophyllite ≥ biotite > sapphirine>orthopyroxene > cordierite.
Characteristic pseudomorph textures indicate coexistence of orthopyroxene and sillimanite during early stages of the reaction history. Assemblages containing orthopyroxene-sillimanite-sapphirine-cordierite-corundum developed during a high-pressure phase of metamorphism and are consistent with equilibration pressures of about 9 kbar at temperatures of 750–800°C. Decompression towards medium-pressure granulite facies generated various sapphirine-bearing assemblages. The diagnostic assemblage of this stage is sapphirine-cordierite. Sapphirine occurs in characteristic symplectite textures. The major mineralogical changes can be described by the discontinuous FMAS reaction: orthopyroxene + sillimanite → sapphirine + cordierite + corundum.
The disequilibrium textures found in the Hasleholmen rocks are characteristic for reactions which have been in progress but then ceased before they run to completion. Textures such as reaction rims, symplectites, partial replacement, corrosion and dissolution of earlier minerals are characteristic of granulite facies rocks. They indicate that, despite relatively high temperatures (700–800° C), equilibrium domains were small and chemical communication and transport was hampered as a result of dry or H2O-poor conditions.  相似文献   

17.
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   

18.
Abstract A deerite-bearing rock occurs at the boundary between quartzite and metabasites within the 'schistes lustrés'of eastern Corsica. It contains the typomorphic assemblage pyroxene, blue amphibole, hematite and magnetite. Pyroxene shows homogeneous composition close to the aegirine end-member and blue amphibole is zoned from crossite core to riebeckite rim. The bulk chemical analysis of the rock is remarkable by its very high iron content and the presence of an unusually large amount of Zn which is concentrated in both deerite and amphibole. Electron microprobe analyses of the Corsican deerite are compared with those published in the literature; as shown by deerite from the Fransciscan iron formation, the principal substitution for Fe2+ is Mn whereas the amount of substitution for Fe3+ is low. In the system SiO2-FeO-Fe2O3-Al2O3-Na2O-MgO-H2O the typomorphic paragenesis can be described by an univariant reaction interpreted as the result of a pressure decrease. P-T conditions of metamorphism, previously estimated to be 8 kbar and 300°C, are in good agreement with present knowledge of the deerite stability field. The occurrence of hematite and magnetite in equilibrium permits an estimation of the oxygen fugacity (log f o2= -29.41 bar). Oxidation conditions are higher than those previously mentioned in the literature for similar assemblages.  相似文献   

19.
Eclogite facies metatroctolites from a variety of Western Alps localities (Voltri, Monviso, Lanzo, Allalin, Zermat–Saas, etc.) that preserve textural evidence of their original form as bimineralic olivine‐plagioclase rocks are considered in terms of calculated mineral equilibria in the system Na2O‐CaO‐FeO‐MgO‐Al2O3‐SiO2‐H2O (NCFMASH). Pseudosections, based on a new petrogenetic grid for NCFMASH presented here, are used to unravel the metamorphic history of the metatroctolites, considering the rocks to consist of different composition microdomains corresponding to the original olivine and plagioclase grains. On the basis that the preservation of the mineral assemblage in each microdomain will tend to be from where on a rock's P–T path the metamorphic fluid phase is used up via rehydration reactions, P–T pseudosections contoured for water content, and P–T path‐MH2O (amount of water) pseudosections, are used to examine fluid behaviour in each microdomain. We show that the different microdomains are likely to preserve their mineral assemblages from different places on the P–T path. For the olivine microdomain, the diagnostic mineral assemblage is chloritoid + talc (+ garnet + omphacite). The preservation of this assemblage, in the light of the closed system P–T path‐MH2O relationships, implies that the microdomain loses its metamorphic fluid as it starts to decompress, and, in the absence of subsequent hydration, the high pressure mineral assemblage is then preserved. In the plagioclase microdomain, the diagnostic assemblage is epidote (or zoisite) + kyanite + quartz suggesting a lower pressure (of about 2 GPa) than for the olivine microdomain. In the light of P–T path‐MH2O relationships, development of this assemblage implies breakdown of lawsonite across the lawsonite breakdown reaction, regardless of the maximum pressure reached. It is likely that the plagioclase microdomain was mainly fluid‐absent prior to lawsonite breakdown, only becoming fluid‐present across the reaction, then immediately becoming fluid‐absent again.  相似文献   

20.
Low-pressure granulite facies metasedimentary gneisses exposed in MacRobertson Land, east Antarctica, include hercynitic spinel-bearing metapelitic gneisses. Peak metamorphic mineral assemblages include spinel + rutile + ilmenite + sillimanite + garnet, spinel + ilmenite + sillimanite + garnet + cordierite, ortho-pyroxene + magnetite + ilmenite + garnet, spinel + cordierite + biotite + ilmenite and orthopyroxene + cordierite + biotite, each with quartz, K-feldspar and melt. The presence of garnet + biotite- and cordierite + orthopyroxene-bearing assemblages implies crossing tie-lines in AFM projection for the K2O-FeO-MgO-Al2O3-SiO2-H2O (KFMASH) system. This apparent contradiction, and the presence of spinel, rutile and ilmenite in the assemblages, is acounted for by using the KFMASH-TiO2-O2 system, i.e. AFM + TiO2+ Fe2O3. We derive a petrogenetic grid for this system, applicable to low-pressure granulite facies metamorphic conditions. Retrograde assemblages are interpreted from corona textures on hercynitic spinel and Fe-Ti oxides. The relative positions of the peak and retrograde metamorphic assemblages on the petrogenetic grid suggest that corona development occurred during essentially isobaric cooling.  相似文献   

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