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1.
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   

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.
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   

4.
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   

5.
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   

6.
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   

7.
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   

8.
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   

9.
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   

10.
Abstract Nearly pure CO2 fluid inclusions are abundant in migmatites although H2O-rich fluids are predicted from the phase equilibria. Processes which may play a role in this observation include (1) the effects of decompression on melt, (2) generation of a CO2-bearing volatile phase by the reaction graphite + quartz + biotite + plagioclase = melt + orthopyroxene + CO2-rich vapour, (3) selective leakage of H2O from CO2+ H2O inclusions when the pressure in the inclusion exceeds the confining pressure during decompression, and (4) enrichment of grain-boundary vapour in CO2 by subsolidus retrograde hydration reactions.  相似文献   

11.
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   

12.
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   

13.
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   

14.
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   

15.
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   

16.
The George Sound Paragneiss (GSP) represents a rare Permo-Triassic unit in Fiordland that occurs as a km-scale pillar to gabbroic and dioritic gneiss of c . 120 Ma Western Fiordland Orthogneiss (WFO). It is distinguished from Palaeozoic paragneiss common in western Fiordland (Deep Cove Gneiss) by SHRIMP and laser-ablation U–Pb ages as young as c . 190 Ma and 176Hf/177Lu >0.2828 for detrital zircon grains. The Mesozoic age of the GSP circumvents common ambiguity in the interpretation of Cretaceous v. Palaeozoic metamorphic assemblages in the Deep Cove Gneiss. A shallowly dipping S1 foliation is preserved in the GSP distal to the WFO, cut by 100 m scale migmatite contact zones. All units preserve a steeply dipping S2 foliation. S1 staurolite and sillimanite inclusions in the cores of metapelitic garnet grains distal to the WFO preserve evidence for prograde conditions of T  <   650 °C and P <  8 kbar. Contact aureole and S2 assemblages include Mg-rich, Ca-poor cores to garnet grains in metapelitic schist that reflect WFO emplacement at ≈760 °C and ≈6.5 kbar. S2 kyanite-bearing matrix assemblages and Ca-enriched garnet rims reflect ≈650 °C and ≈11 kbar. Poorly oriented muscovite–biotite intergrowths and rare paragonite reflect post-S2 high- P retrogression and cooling. Pseudosection modelling in NCKFMASH defines a high- P anti-clockwise P–T history for the GSP involving: (i) mid- P amphibolite facies conditions; preceding (ii) thermal metamorphism adjacent to the WFO; followed by (iii) burial to high- P and (iv) high- P cooling induced by tectonic juxtaposition of cooler country rock.  相似文献   

17.
Abstract Chloritoid-bearing metasedimentary rocks occur in close proximity to blueschists and eclogites in the Tertiary high-pressure metamorphic belt of northern New Caledonia. The typical assemblage of chloritoid-bearing rocks in the epidote zone is quartzchlorite-muscovite-garnet-chloritoid. In the omphacite zone, epidote is an additional member of the chloritoid-bearing assemblage. Paragonite is rare, plagioclase was not detected, and rutile and ilmenite are the Fe-Ti oxide phases. Chloritoid-glaucophane is not a common assemblage. Chloritoid-bearing rocks have relatively low (Ca+K+Na)/Al ratios and the chloritoids are relatively Mg-rich with Mg/ (Mg+Fe) up to about 0.4. A comparison of the mineral assemblages and mineral chemistry with experimental and computed phase equilibria suggest an upper temperature limit near 560° C in the omphacite zone and a minimum temperature limit near 450° C at 10 kbar. An empirical garnet-chlorite Fe-Mg exchange thermometer does not yield consistent results for the higher-grade rocks, suggesting T s ranging from 390 to 535° C in the omphacite zone and 420–465° C in the epidote zone. The distribution coefficient K D = (Fe/Mg)ctd/(Fe/Mg)chl for chloritoid and chlorite ranges from 3.9 to 6.4, values which are lower than those (=10) from lower greenschist facies rocks, but are near those of upper greenschist facies and albite-epidote amphibolite facies.  相似文献   

18.
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   

19.
Sapphirine, coexisting with quartz, is an indicator mineral for ultrahigh‐temperature metamorphism in aluminous rock compositions. Here a new activity‐composition model for sapphirine is combined with the internally consistent thermodynamic dataset used by THERMOCALC, for calculations primarily in K2O‐FeO‐MgO‐Al2O3‐SiO2‐H2O (KFMASH). A discrepancy between published experimentally derived FMAS grids and our calculations is understood with reference to H2O. Published FMAS grids effectively represent constant aH2O sections, thereby limiting their detailed use for the interpretation of mineral reaction textures in compositions with differing H2O. For the calculated KFMASH univariant reaction grid, sapphirine + quartz assemblages occur at P–T in excess of 6–7 kbar and 1005 °C. Sapphirine compositions and composition ranges are consistent with natural examples. However, as many univariant equilibria are typically not ‘seen’ by a specific bulk composition, the univariant reaction grid may reveal little about the detailed topology of multi‐variant equilibria, and therefore is of limited use for interpreting the P–T evolution of mineral assemblages and reaction sequences. Calculated pseudosections, which quantify bulk composition and multi‐variant equilibria, predict experimentally determined KFMASH mineral assemblages with consistent topology, and also indicate that sapphirine stabilizes at increasingly higher pressure and temperature as XMg increases. Although coexisting sapphirine and quartz can occur in relatively iron‐rich rocks if the bulk chemistry is sufficiently aluminous, the P–T window of stability shrinks with decreasing XMg. An array of mineral assemblages and mineral reaction sequences from natural sapphirine + quartz and other rocks from Enderby Land, Antarctica, are reproducible with calculated pseudosections. That consistent phase diagram calculations involving sapphirine can be performed allows for a more thorough assessment of the metamorphic evolution of high‐temperature granulite facies terranes than was previously possible. The establishment of a a‐x model for sapphirine provides the basis for expansion to larger, more geologically realistic chemical systems (e.g. involving Fe3+).  相似文献   

20.
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   

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