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1.
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   

2.
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   

3.
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   

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.
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   

6.
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   

7.
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   

8.
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   

9.
Abstract: Transportation of various kinds of elements occurred in wall rocks (Quaternary andesites) during the hydrothermal alteration accompanied by the Hishikari epithermal gold mineralization. For example, K2O and MgO contents of wall rocks decrease away from the gold-quartz veins, while (CaO+Na2O) content increases, and SiO2 content is variable near the veins. Hydrothermal alteration zoning and bulk compositional variations in wall rocks suggest that the mixing of hydrothermal solution and acidic groundwater took place an important role as the cause for the hydrothermal alteration and bulk compositional variations. The relationship between dissolved silica concentration and temperature of hydrothermal solution mixed with groundwater is obtained based on precipitation kinetics-fluid flow–mixing model, and the computed results are compared with the distribution of SiO2 minerals (quartz and cristobalite) in the hydrothermal alteration zones. This comparison suggests that the most reasonable flow rate of fluids migrating through hydrothermal alteration zones, and A/M (A: surface area of rocks interacting with fluid, M: mass of fluid) are estimated to be ca. 10-4.2 m/sec, and ca. 0.10 m2/kg, respectively. The mixing of two fluids (hydrothermal solution and acidic groundwater) can also explain δ18O zoning in the altered country rocks, hydrothermal alteration zoning from K-feldspar through K-mica to kaolinite from the center (veins) to margin, and deposition of gold.  相似文献   

10.
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   

11.
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   

12.
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   

13.
Garnet from a kinzigite, a high-grade gneiss from the central Black Forest (Germany), displays a prominent and regular retrograde diffusion zoning in Fe, Mn and particularly Mg. The Mg diffusion profiles are suitable to derive cooling rates using recent datasets for cation diffusion in garnet. This information, together with textural relationships, thermobarometry and thermochronology, is used to constrain the pressure–temperature–time history of the high-grade gneisses. The garnet–biotite thermometer indicates peak metamorphic temperatures for the garnet cores of 730–810  °C. The temperatures for the outer rims are 600–650  °C. Garnet–Al2SiO5–plagioclase–quartz (GASP) barometry, garnet–rutile–Al2SiO5–ilmenite (GRAIL) and garnet–rutile–ilmenite–plagioclase–quartz (GRIPS) barometry yield pressures from 6–9  kbar. U–Pb ages of monazite of 341±2  Ma date the low- P high- T metamorphism in the central Black Forest. A Rb/Sr biotite–whole rock pair defines a cooling age of 321±2  Ma. The two mineral ages yield a cooling rate of about 15±2  °C Ma−1. The petrologic cooling rates, with particular consideration of the f O2 conditions for modelling retrograde diffusion profiles, agree with the geochronological cooling rate. The oldest sediments overlying the crystalline basement indicate a minimum cooling rate of 10  °C Ma−1.  相似文献   

14.
Abstract In granulite facies metapelitic rocks in the Musgrave Complex, central Australia, reaction between S1 garnet and sillimanite involves the development in S2 of both garnet + cordierite + hercynitic spinel + biotite and hercynitic spinel + cordierite + sillimanite + biotite. The S2 assemblages occur either in coronas and symplectites, mainly around garnet, or, in rocks in which S2 is more strongly developed, as recrystallized assemblages. Ignoring the presence of biotite and ilmenite, the mineral textures can be accounted for qualitatively by a consideration of the model system FeO-MgO-Al2O3-SiO2 (FMAS); the textural relationships accord with decompression accompanying the change from S1 to S2. However, since biotite and ilmenite are involved in the assemblages, the parageneses are better accounted for in terms of equilibria in the expanded model system K2O-FeO-MgO-Al2O3-SiO2-H2-TiO2-Fe2O3 (KFMASHTO), i.e. AFM + TiO2+ Fe2O3. The coronas reflect the tectonic unroofing of at least part of the Musgrave Complex from peak S1 conditions of about 8 kbar to S2 conditions of about 4 kbar.  相似文献   

15.
Abstract. The Jecheon granitoids, having an elongated shape of NE-SW 27 km and NW-SE 13 km (190 km2), are composed mostly of magnetite-series hornblende-biotite granodiorite and biotite granite, which intrude into the Neoproterozoic metamor-phic and Paleozoic sedimentary rocks of the Ogcheon Belt. The granitoids have Triassic-Jurassic age of 202.7 ±1.9 Ma with very high 87Sr/86Sr initial ratio of 0.7140. The granodiorite has 63–69 % SiO2, 15.1–17.3 % Al2O3, <1.6 % MgO, 6–15 ppm Y and Sr/Y ratios of 24–76, and is depleted in HREE. Biotite granite together, the Jecheon pluton has adakitic characteristics, which are unique in a continental tectonic setting. The granitoids may have been generated by partial melting of an older adakitic granitoid of I-type basement, or by separation of early crystallized garnet and hornblende from an anatectic melt.  相似文献   

16.
Abstract. The Cerro Colorado intrusive stock in the northeastern Chilean Precordillera is a plutonic complex formed during Late Cretaceous (64–72 Ma), and consists predominantly of pyroxene-bearing biotite monzogabbro (Colorado Unit), with lesser amounts of pyroxene-bearing hornblende biotite diorite (Pucaquisca Unit) and biotite hornblende monzonite (Pabellón Unit). Compositional variations of major and trace elements suggest that the Cerro Colorado complex is composed of shoshonitic alkali granitoids generated at the active continental margin. The basic to intermediate rocks of the Colorado Unit are characterized by high contents of A12O3 (>20 wt%), CaO and LIL elements (K, Sr, Ba), high Fe/Mg ratio and fairly low contents of Cr, Ni and Y. These characteristics suggest that the Colorado Unit was formed by plagioclase-free source magma originated from asthenospheric mantle or mafic lower crust. All the Cerro Colorado rocks generally display linear compositional trends, and the latest Pabellón Unit rocks are richer in SiO2 than the Colorado Unit and Pucaquisca Unit rocks. These indicate that the Pabellón Unit rocks were produced by assimilation-fractional crystallization process of the basic to intermediate magma genetically related to the voluminous Colorado Unit.  相似文献   

17.
Abstract: The Karlapat bauxite deposit occurs in the Eastern Ghat Group of rocks in Orissa and has developed in the khondalites. Mineralogical and physical observations on bore hole samples reflect the presence of a maximum of six weathered zones from top to bottom. These zones are termed as topsoil, siliceous laterite, ferruginous laterite, bauxite, lithomarge and altered khondalite. Four-dimensional trend surface models are developed for the data of 45 and 36 bore holes from north and south blocks, respectively, on Al2O3 and SiO2 to delineate the zones of metallurgical grade bauxite (SiO25 % and Al2O340 %). The results indicate about 15 m thickness of bauxite in the north block while it could be up to 20 m thick in the south block, leaving about 10 m of lat-erites at the top of each block. High grade bauxite (>47 % Al2O3) is also encountered at specific locations.  相似文献   

18.
The pressure dependence of the zirconium-in-rutile thermometer   总被引：19，自引：1，他引：19  
The solubility of ZrO2 in rutile is strongly temperature-dependent and has been identified as a potentially powerful thermometer when the rutile coexists with an appropriate buffer assemblage, e.g. zircon + quartz. In combination with experimental data at 10 kbar, previous consideration of data on natural rutile has not identified a pressure dependence for the thermometer. However, the expected volume change as a result of substitution of the larger Zr4+ cation for Ti4+ suggests that the Zr content of rutile should decrease with increasing pressure. To investigate the pressure dependence of the thermometer, piston cylinder (at 10, 20 & 30 kbar) and 1 atm furnace experiments were performed in the system ZrO2-TiO2-SiO2. The solubility of ZrO2 in rutile, in the presence of zircon and quartz was reversed at each pressure value. From these experiments, the thermodynamics of the end-member reaction ZrSiO4 = SiO2 + ZrO2 (in rutile) have been determined. There is a secondary pressure effect accompanying the primary temperature dependence of the Zr content of rutile. New thermometer equations are, in the α -quartz field: in the β -quartz field and in the coesite field in which φ is ppm Zr, P is in kbar and R is the gas constant, 0.0083144 kJ K−1. Thermometric results using these equations are shown for a range of geological settings.  相似文献   

19.
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   

20.
The 5-km deep Chinese Continental Scientific Drilling Main Hole penetrated a sequence of ultrahigh pressure (UHP)-metamorphic rocks consisting mainly of eclogite, gneiss and garnet-peridotite with minor schist and quartzite. Zircon separates taken from thin layers of schist and gneiss within eclogite were investigated. Cathodoluminescence images of zircon grains show that they have oscillatory zoned magmatic cores and unzoned to patchy zoned metamorphic rims. Zircon rims contain rare coesite and calcite inclusions whereas cores contain inclusions of both low- P minerals (e.g. feldspar, biotite and quartz) and coesite and other eclogite-facies minerals such as phengite and jadeite. The zircon cores give highly variable 206Pb/238U ages ranging from 760 to 431 Ma for schist and from 698 to 285 Ma for gneiss, and relatively high but variable Th/U ratios (0.16–1.91). We suggest that the coesite and other eclogite facies mineral inclusions in zircon cores were not magmatic but formed through metasomatic processes caused by fluids during UHP metamorphism, and that the fluids contain components of SiO2, Al2O3, K2O, FeO, MgO, Na2O and H2O. Metasomatism of the Sulu UHP rocks during continental subduction to mantle depths has partly altered magmatic zircon cores and reset isotopic systems. This study provides key evidence that mineral inclusions within magmatic zircon domains are not unequivocal indicators of the formation conditions of the respective domain. This finding leads us to conclude that the routine procedure for dating of metamorphic events solely based on the occurrence of mineral inclusions in zoned zircon could be misleading and the data should be treated with caution.  相似文献   

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