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1.
Thermochemical data on several phases forming in the systemCaO-MgO-Al2O3-SiO2 have been tested for consistency in reproducingexperimental phase equilibrium relationships. Calorimetric dataon enthalpy, entropy and heat capacity have been adjusted withinexperimental errors and new data on some phases have been estimatedusing phase equilibrium data. The consistency of the data inreproducing phase equilibrium relations in the multicomponent-multiphasesystems has been tested by computing phase diagrams using themethod of minimization of total Gibbs free energy. The recentcalorimetric data on most phases can be used without any significantchange except for phases that show cation disorder. Disordercorrections have been added to the heat capacity data on gehlenite,anorthite, spinel and Ca-Tschermak.  相似文献   

2.
The enthalpy of drop-solution in molten 2PbO·B2O3 of synthetic and natural lawsonite, CaAl2(Si2O7)(OH)2·H2O, was measured by high-temperature oxide melt calorimetry. The enthalpy of formation determined for the synthetic material is (fHOxides=-168.7Dž.4 kJ mol-1, or (fH0298=-4,872.5dž.0 kJ mol-1. These values are in reasonable agreement with previously published data, although previous calorimetric work yielded slightly more exothermic data and optimisation methods resulted in slightly less exothermic values. The equilibrium conditions for the dehydration of lawsonite to zoisite, kyanite and quartz/coesite at pressures and temperatures up to 5 GPa and 850 °C were determined by piston cylinder experiments. These results, other recent phase equilibrium data, and new calorimetric and thermophysical data for lawsonite and zoisite, Ca2Al3(SiO4)(Si2O7)O(OH), were used to constrain a mathematical programming analysis of the thermodynamic data for these two minerals in the chemical system CaO-Al2O3-SiO2-H2O (CASH). The following data for lawsonite and zoisite were obtained: (fH0298 (lawsonite)=-4,865.68 kJ mol-1 , S0298 (lawsonite)=229.27 J K-1 mol-1 , (fH0298 (zoisite)=-6,888.99 kJ mol-1 , S0298 (zoisite)=297.71 J K-1 mol-1 . Additionally, a recalculation of the bulk modulus of lawsonite yielded K=120.7 GPa, which is in good agreement with recent experimental work.  相似文献   

3.
Chromium as Cr3+ substitutes for octahedrally coordinated Alin upper-mantle minerals, thereby reducing the activity of Al2O3in the system and hence the concentration of Al2O3 in partialmelts. The effect of Cr2O3 on melt compositions multiply saturatedwith the spinel lherzolite phase assemblage has been quantifiedin the system CaO–MgO–Al2O3–SiO2–Cr2O3at 1·1 GPa as a function of 100 Cr/(Cr + Al) in the spinel(Cr#sp). The decrease of Al2O3 in the melt with increasing Cr#spis accompanied by increasing MgO and SiO2, whereas CaO remainsalmost constant. Consequently, the CaO/Al2O3 ratio of the meltincreases with Cr#sp, and the melt becomes richer in normativediopside, hypersthene and quartz. The effect may explain certainmantle melts with unusually high CaO/Al2O3 ratios. The concentrationof Cr2O3 in the melt remains low even at high Cr#sp, which meansthat the strong effect of Cr2O3 on partial melting equilibriais not readily apparent from its concentration in the melt itself.The existence of a highly refractory major component such asCr2O3 nullifies simplified conclusions from the ‘inverseapproach’ in the experimental study of basalt petrogenesis,as there is insufficient information in the composition of thepartial melt to reconstruct the conditions of melting. KEY WORDS: basalt petrogenesis; partial melting; reversal experiment; spinel lherzolite; system CMAS–Cr2O3; CaO/Al2O3 of melt; effect of Cr2O3  相似文献   

4.
The problem of deriving an optimal set of thermodynamic propertiesof minerals from a diverse experimental data base is reviewedand a preferred methodology proposed. Mathematical pro-gramming(MAP)methods extend the linear programming (LIP) approach first presentedby Gordon (1973), and make it possible to account for the typeof information conveyed, and the uncertainties attending bothphase equilibrium data and direct measurements of phase properties.For phase equilibrium data which are (in most cases) characterizedby non-normal error distributions across experimental brackets,the midpoint of a bracket is no more probable than other points,and the data are best treated by considering the inequalityin the change in Gibbs free energy of reaction at each half-bracket.Direct measurements of phase properties can be assumed to haveapproximately normal error distributions, and the MAP techniqueoptimizes agreement with these values by using the principlesof least squares in the definition of an objective function.The structure of this problem, treatment of uncertainties invarious types of experimental data, and method of optimizingfinal solutions are discussed in some detail.The method is appliedto experimental data in the MgO-SiO2-H2O system, where inconsistenciesamong the data are resolved and an optimal set of thermodynamicproperties is presented. The derived standard state entropiesand volumes agree with all direct measurements (within theiruncertainties), as do enthalpies of formation from the elementsexcept for those of talc (+16 kJ mol–1), anthophyllite(+ 14 kJ mol–1), and brucite (–1 kJ mol–1).Stable phase relations in the system have the topology predictedby Greenwood (1963, 1971), with quartz- and forsterite-absentinvariant points at 683 ?C-6-4 kb and 797 ?C-12 kb respectively,repeating at 552 ?C-120 b and 550 ?C-55 b. The thermodynamicanalysis indicates little remaining flexibility in the phaserelations, which, when combined with suitable activity modelsfor solid solution, should allow for accurate determinationof the conditions of metamorphism of ultramafic rocks.  相似文献   

5.
The system Ca2Al3Si3O11(O/OH)-Ca2Al2FeSi3O11(O/OH), with emphasis on the Al-rich portion, was investigated by synthesis experiments at 0.5 and 2.0 GPa, 500-800 °C, using the technique of producing overgrowths on natural seed crystals. Electron microprobe analyses of overgrowths up to >100 µm wide have located the phase transition from clinozoisite to zoisite as a function of P-T-Xps and a miscibility gap in the clinozoisite solid solution. The experiments confirm a narrow, steep zoisite-clinozoisite two-phase loop in T-Xps section. Maximum and minimum iron contents in coexisting zoisite and clinozoisite are given by Xpszo (max) = 1.9*10 - 4 T+ 3.1*10 - 2 P - 5.36*10 - 2{\rm X}_{{\rm ps}}^{{\rm zo}} {\rm (max) = 1}{\rm .9*10}^{ - 4} T{\rm + 3}{\rm .1*10}^{ - 2} P - {\rm 5}{\rm .36*10}^{ - 2} and Xpsczo (min) = (4.6 * 10 - 4 - 4 * 10 - 5 P)T + 3.82 * 10 - 2 P - 8.76 * 10 - 2{\rm X}_{{\rm ps}}^{{\rm czo}} {\rm (min)} = {\rm (4}{\rm .6} * {\rm 10}^{ - {\rm 4}} - 4 * {\rm 10}^{ - {\rm 5}} P{\rm )}T + {\rm 3}{\rm .82} * {\rm 10}^{ - {\rm 2}} P - {\rm 8}{\rm .76} * {\rm 10}^{ - {\rm 2}} (P in GPa, T in °C). The iron-free end member reaction clinozoisite = zoisite has equilibrium temperatures of 185ᇆ °C at 0.5 GPa and 0ᇆ °C at 2.0 GPa, with (Hr0=2.8ǃ.3 kJ/mol and (Sr0=4.5ǃ.4 J/mol2K. At 0.5 GPa, two clinozoisite modifications exist, which have compositions of clinozoisite I ~0.15 to 0.25 Xps and clinozoisite II >0.55 Xps. The upper thermal stability of clinozoisite I at 0.5 GPa lies slightly above 600 °C, whereas Fe-rich clinozoisite II is stable at 650 °C. The schematic phase relations between epidote minerals, grossular-andradite solid solutions and other phases in the system CaO-Al2O3-Fe2O3-SiO2-H2O are shown.  相似文献   

6.
The experimental work on biotites has primarily involved compositionsalong the annite-phlogopite join, but most natural biotitescontain significantly larger amounts of aluminum. At the sametime, the aluminum content of natural biotites varies considerably.The available evidence indicates that these variations in thealuminum content of biotite depend on the conditions of formationand the whole rock chemistry. Experiments on the phase relations of aluminous iron biotitesin the silica deficient system KAlSiO4-KAlSi3O8-Al2O3-Fe-O-H(pfluid = 2 kb) indicate that compositions up to Ann75 can besynthesized on the join annite [K2Fe6Al2Si6O20(OH)4]-aluminumbiotite [K2Al6Al2Al6O20(OH)4]. The aluminous biotites are stableto higher temperatures than annite. An isobaric divariant equilibrium,Bioss-Mtss-Sa-Lc-V, extends to higher oxygen fugacities fromthe Ann-Mt-Sa-Lc-V curve of Eugster & Wones (1962). Compositioncontours on this surface indicate that both the magnetite andbiotite become more aluminous with increasing temperature and/oroxygen fugacity. The Bioss-Mtss-Sa-Lc-V reaction surface isterminated by equilibria involving the additional phases muscovite,corundum, and hercynite respectively as the conditions becomemore reducing. At 2 kb fluid pressure; aluminum-rich iron biotiteis stable to 555 °C on the HM buffer, 763 °C on theMt-Hc-Cor buffer, 820 °C on NNO, and about 860 °C onQFM. The data obtained can be applied to a number of biotitesyenites and appears to explain why iron-rich aluminum biotitesoccur in these rocks.  相似文献   

7.
In the system CaO-MgO-Al2O3-SiO2-Na2O-H2O under 5 kb pressurethe invariant equilibrium forsterite-orthopyroxene-Ca-rich clinopyroxene-amphibole-plagioclase-liquid-vapourhas been identified at 960?12 ?C. A similar invariant assemblagewith spinel replacing Ca-rich clinopyroxene exists at 950?8?C. The liquid in the former equilibrium contains 16.5 per cent(wt.) normative quartz and 3 per cent Na2O; the plagioclaseis more calcic than An87; the pyroxenes contain about 3 percent Al2O3 and the amphibole is hypersthene-normative. Two anhydrousthermal maxima, the olivine-Ca-rich clinopyroxene-plagioclaseand the orthopyroxene-Ca-rich clinopyroxene-plagioclase dividezones are not encountered in this system, and nepheline-normativeliquids may crystallize amphibole?olivine?Ca-rich clinopyroxeneto produce quartz-normative residual liquids of andesite-typecomposition. A thermal maximum involving amphibole-olivine-Ca-richclinopyroxene-liquid-vapour exists for liquids containing approximately11 per cent normative nepheline and liquids more undersaturatedthan this will crystallize these phases to produce extremelynephelinitic liquids. Phase diagrams are presented which facilitate the predictionof crystallization sequences and liquid evolution paths forany basic or intermediate composition under the conditions employedhere.  相似文献   

8.
Activity diagrams in the system KAlSi3O8-NaAlSi3O8-Al2SiO5-SiO2-H2O-HClhave been calculated in terms of aK+/aH+ and aN+/aH+ from existingexperimental data. They show the effect of temperature, pressure,and aH2O on the stability fields of the alkali feldspars, micas,and aluminium silicate. These activity diagrams are useful in revealing the bufferingcapacity of mineral assemblages and the chemical potential gradientsestablished by changes in T, P, aH2O, and mineral assemblage.An analysis of mineral paragenesis in terms of these diagramssuggests that mosaic equilibrium, allowing limited metasomatismand internal buffering of chemical potentials, best describemetamorphic systems. Thus the dehydration reaction: muscovite+quartz=K-feldspar+Al2SiO5+H2O which is most important in closed systems, probably fails todescribe in detail the mechanism of natural muscovite decomposition.Rather the decomposition of muscovite is more likely representedby ionic reactions. The replacement of muscovite by feldspar: muscovite+6 SiO2+2 K+=3 K-feldspar+2 H+ muscovite+6 SiO2+3 Na+=3 Albite+K++2 H+ is favored at high temperature and low pressure, and may accountfor the crystallization of some feldspars in metamorphic rocks.The reaction involving aluminium silicate replacement of muscovite: 2 muscovite+2 H+=3 Al2SiO5+3 SiO2+3 H2O+2 K+ is favored at high temperature and pressure and low aH2O, andcould contribute to the development of the aluminium silicates.It is concluded that both activity diagrams and AKNa projectionsshould be used together to more completely evaluate mineralparagenesis in terms of mosaic equilibria.  相似文献   

9.
A thermodynamic model is proposed for calculation of liquidus relations in multicomponent systems of geologic interest. In this formulation of mineral-melt equilibria, reactions are written in terms of the liquid oxide components, and balanced on the stoichiometry of liquidus phases. In order to account for non-ideality in the liquid, a ‘Margules solution’ is derived in a generalized form which can be extended to systems of any number of components and for polynomials of any degree. Equations are presented for calculation of both the excess Gibbs free energy of a solution and the component activity coefficients.Application to the system CaO-Al2O3-SiO2 at one atmosphere pressure is achieved using linear programming. Thermodynamic properties of liquidus minerals and the melt are determined which are consistent with adopted error brackets for available calorimetric and phase equilibrium data. Constraints are derived from liquidus relations, the CaO-SiO2 binary liquid immiscibility gap, solid-solid P-T reactions, and measured standard state entropies, enthalpies, and volumes of minerals in this system.Binary and ternary liquidus diagrams are recalculated by computer programs which trace cotectic boundaries and isothermal sections while checking each point on a curve for metastability. The maximum differences between calculated and experimentally determined invariant points involving stoichiometric minerals are 17°C and 1.5 oxide weight per cent. Because no solid solution models have been incorporated, deviations are larger for invariant points which involve non-stoichiometric minerals.Calculated heats of fusion, silica activities in the melt, and heats of mixing of liquids compare favorably with experimental data, and suggest that this model can be used to supplement the limited amount of available data on melt properties.  相似文献   

10.
ROSE  N. M.; BIRD  D. K. 《Journal of Petrology》1987,28(6):1193-1218
Layered gabbros at Nordre Aputit?q and Kruuse Fjord were emplacedduring extensional tectonism that led to the formation of theNorth Atlantic basin in the Early Tertiary. Sub-solidus reactionsbetween the gabbros and hydrothermal fluids formed superimposedalteration assemblages in fractures, cavities, and the adjacentgabbros. The earliest secondary minerals are Ca-Al amphibole+ clinopyroxene + biotite ? plagioclase that form thin veinsor porous pegmatitic masses. These minerals are crosscut, overgrownor partially replaced by one or more generations of prehniteand epidote bearing assemblages associated with filling of thefractures and cavities, and with extensive wall rock albitization. Wide variations in the partitioning of Fe3+ and Al between coexistingprehnite and epidote solid solutions occur in these alteredgabbros. The partitioning data define distinct clusters in termsof associated mineralogy and paragenetic relations. This, togetherwith prehnite and epidote compositions from active geothermalsystems, are used to evaluate the thermodynamic properties ofthe intercrystalline exchange reaction:When compared to thecompositions of prehnite and epidote in the Nordre Aputit?qand Kruuse Fjord intrusions, it is concluded that the latestand lowest temperature generations of prehnite and epidote displaydisequilibrium partitioning of Fe3+ and Al, manifested by theoccurrence of prehnite that is relatively enriched in Fe3+ Thermodynamic analysis of phase relations in the system Na2O-CaO-Al2O3-Fe2O3-FeO-SiO2-H2O-HClis used to determine local equilibrium constraints on Fe3+-Alsubstitution in prehnite and epidote. It appears that parageneticand compositional relations of prehnite and epidote are sensitiveindicators of local fluctuations in fluid composition and temperature.The complex magmatic and structural history of the gabbros atNordre Aputit?q relative to Kruuse Fjord is considered to beresponsible for the differences in mineral paragenesis and compositionsof prehnite and epidote within these intrusions.  相似文献   

11.
The recent publication of an updated thermodynamic dataset for petrological calculations provides an opportunity to illustrate the relationship between experimental data and the dataset, in the context of a new set of activity–composition models for several key minerals. These models represent orthopyroxene, clinopyroxene and garnet in the system CaO–MgO–Al2O3–SiO2 (CMAS), and are valid up to 50 kbar and at least 1800 °C; they are the first high‐temperature models for these phases to be developed for the Holland & Powell dataset. The models are calibrated with reference to phase‐relation data in the subsystems CaO–MgO–SiO2 (CMS) and MgO–Al2O3–SiO2 (MAS), and will themselves form the basis of models in larger systems, suitable for calculating phase equilibria in the crust and mantle. In the course of calibrating the models, it was necessary to consider the reaction orthopyroxene + clinopyroxene + spinel = garnet + forsterite in CMAS, representing a univariant transition between simple spinel and garnet lherzolite assemblages. The high‐temperature segment of this reaction has been much disputed. We offer a powerful thermodynamic argument relating this reaction to the equivalent reaction in MAS, that forces us to choose between good model fits to the data in MAS or to the more recent data in CMAS. We favour the fit to the MAS data, preserving conformity with a large body of experimental and thermodynamic data that are incorporated as constraints on the activity–composition modelling via the internally consistent thermodynamic dataset.  相似文献   

12.
The pressure-temperature-compositional (P-T-X) dependence ofthe solubility of Al2O3 in orthopyroxene coexisting with garnethas been experimentally determined in the P-T range 5–30kilobars and 800–1200 ?C in the system FeO—MgO—Al2O3—SiO2(FMAS). These results have been extended into the CaO—FeO—MgO—Al2O3—SiO2(CFMAS) system in a further set of experiments designed to determinethe effect of the calcium content of garnet on the Al2O3 contentsof coexisting orthopyroxene at near-constant Mg/(Mg + Fe). Startingmaterials were mainly glasses of differing Mg/(Mg + Fe) or Ca/(Ca+ Mg + Fe) values, seeded with garnet and orthopyroxene of knowncomposition, but mineral mixes were also used to demonstratereversible equilibrium. Experiments were performed in a piston-cylinderapparatus using a talc/pyrex medium. Measured orthopyroxene and corrected garnet compositions werefitted by multiple and stepwise regression techniques to anequilibrium relation in the FMAS system, yielding best-fit,model-dependent parameters Goy= –5436 + 2.45T cal mol–1,and WM1FeA1= –920 cal mol–1. The volume change ofreaction, Vo, the entropy change, So970 and the enthalpy changeHo1,970, were calculated from the MAS system data of Perkinset al. (1981) and available heat capacity data for the phases.Data from CFMAS experiments were fitted to an expanded equilibriumrelation to give an estimate of the term WgaCaMg = 1900 ? 400cal/mole cation, using the other parametric values already obtainedin FMAS. The experimental data allow the development of a arnet-orthopyroxenegeobarometer applicable in FMAS and CFMAS: where This geobarometer is applicable to both pelitic and metabasicgranulites containing garnet orthopyroxene, and to garnet peridoditeand garnet pyroxenite assemblages found as xenoliths in diatremesor in peridotite massifs. It is limited, however, by the necessityof an independent temperature estimate, by errors associatedwith analysis of low Al2O3 contents in orthopyroxenes in high-pressureor low-temperature parageneses, and by uncertainties in thecomposition of garnet in equilibrium with orthopyroxene. Ananalysis of errors associated with this formulation of the geobarometersuggests that it is subject to great uncertainty at low pressuresand for Fe-rich compositions. The results of application ofthis geobarometer to natural assemblages are presented in acompanion paper.  相似文献   

13.
Tourmaline has been synthesized hydrothermally at 200 MPa between 300 and 700 °C from oxide mixtures with Mg-Al ratios for the end members dravite NaMg3Al6(Si6O18)(BO3)3(OH)3(OH) and Mg-foitite &ding6F;(Mg2Al)Al6 (Si6O18)(BO3)3(OH)3(OH). Six different Na concentrations were investigated to determine the distribution of Na between tourmaline and fluid in the SiO2-saturated system Na2O-MgO-Al2O3-SiO2-B2O3-H2O-HCl. Synthetic tourmaline ranges from X-site vacant (&ding6F;) tourmaline (Mg-foitite) to nearly ideal dravite with Na=0.95 apfu. There are small, but significant, amounts of proton deficiency and negligible tetrahedral Al. Chemical variation is primarily caused by the substitutions Al&ding6F;Mg-1Na-1 and minor AlMg-1H-1. Varying amounts of Na and &ding6F; determine the Mg/Al ratios. Besides tourmaline and quartz, additional Mg-Al phases are chlorite and, at 700 °C, cordierite. Albite is also present at high Na concentrations in the bulk composition. The c dimension of the tourmaline crystals increases with Na in tourmaline. The amount of Na in the X-site depends strongly on the bulk concentration of Na in the system as well as on the temperature. These factors in turn control the phase assemblage and the composition of the fluid phase. For the assemblage tourmaline + quartz + chlorite/cordierite + fluid, a linear relationship exists between Na concentration in the fluid (quenched after the run) and tourmaline with temperature: T °C [ᆭ °C]=(Nafluid/Natur)앾.878-14.692 (r2=0.96). For the assemblage tourmaline + albite + quartz + fluid, it is: T °C [ᆣ °C]=(Nafluid/Natur)욝.813-6.231 (r2=0.95), where Nafluid is the concentration of Na+ in the final fluid (mol/l) and Natur is the number of Na cations in the X-site of tourmaline. The equations are valid in the temperature range of 500-715 °C. Our experiments demonstrate that the occupancy of the X-site in combination with the changing concentrations of Al and Mg can be used to monitor changes in the fluid composition in equilibrium with a growing tourmaline crystal. Currently, this relation can be applied qualitatively to natural tourmaline to explain zoning in Na- and Al/(Al+Mg).  相似文献   

14.
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   

15.
Subsolidus and liquidus phase relations along the join MgSiO3—CaMgSi2O6have been determined from the results of dry and hydrothermalruns. Two-pyroxene mixtures which crystallize within the solvusin dry runs form cryptoperthites, and X-ray methods must beused to determine their compositions and locate the boundariesof the solvus. Mg-rich and Ca-rich pyroxenes can, however, bedistinguished in well-crystallized hydrothermal runs by opticaltechniques. The results obtained indicate that solid solution along thisjoin is more restricted than was found by Atlas (1952). Thesolvus intersects the solidus over a composition interval of42 wt per cent. Additional data on the rhombic enstatite protoenstatiteinversion are consistent with Atlas's value of 985??10?C. Thisinversion has proved to be very sensitive to pressure, and thedT/dP slope of the transition is 84??10?/kb. The crystallization of natural pyroxenes from basaltic magmasis reviewed in the light of the experimental data. The solidsolution shown by Fe-poor pyroxene pairs from layered intrusionssuch as the Skaergaard is remarkably restricted. The temperatureof crystallization of these pyroxenes as deduced from the solvuson the join MgSiO3—CaMgSi2O6 is about 1000? C. In makingthis estimate it is assumed that any subsolidus exsolution hasnot proceeded beyond the stage of lamellae formation. This temperatureis below the dry solidus of basalt, and the result indicatesthat either the solid solution shown by these natural pyroxenesis influenced by impurities such as Al or Fe', or the meltinginterval of the magmas which formed the intrusions was loweredby a substantial vapor pressure of H2O. It is suggested that pyroxenes which have crystallized fromextrusive basalts and which have compositions that plot in thecentral portion of the pyroxene quadrilateral are metastablesolid solutions formed by quick cooling. Available informationis not sufficient to clarify the relationship between pigeoniteand the various polymorphs of MgSiO3. It is probable, however,that there is a first-order inversion between pigeonite andprotoenstatite, and possible phase relations between these formsin the system MgSiO3—FeSiO3 are discussed.  相似文献   

16.
SEIFERT  F. 《Journal of Petrology》1970,11(1):73-100
The equilibrium temperatures of the reaction muscovite+chlorite+quartz= cordierite+phlogopite+H2O (1) in the pure system K2O—MgO—Al2O2—SiO2—H2Owere found to be 495±10°C at 1 kb PH2O; 525±10°Cat 2 kb; 610±15°C at 5 kb; 635±10°C at6 kb. From intersection of this curve with the lower temperaturestability limit of cordierite close to 645°C, 6.5 kb PH2O,a reaction cordieritc+muscovite = phlogopite+aluminum silicate+quartz+H2O(2) is generated which has a negative slope and passes throughthe points 645°C, 6.5 kb PH2O and 700°C, 5 kb PH2O.On the high-pressure side of this reaction curve cordieriteis restricted to K2O—poor bulk compositions. Application of the experimentally determined phase relationsto more complex natural pelitic rocks suggests that reaction(1) represents maximum temperatures for the disappearance ofchlorite from pelitic assemblages containing muscovite and quartz,whereas reaction (2) gives maximum water pressures for the disappearanceof cordierite from these rocks.  相似文献   

17.
The kinetic problems associated with the experimental determination of reactions among complex solidsolution phases at low temperatures have hindered our understanding of the phase relations in greenschist facies rocks. In the absence of reliable experimental data, we have used the new, expanded internally-consistent thermodynamic dataset of Holland and Powell (1990), to present calculated phase equilibria for the system CaO–FeO–MgO–Al2O3–SiO2–H2O–CO2 (CaFMASCH) with quartz in eccess, in the range 400°–500°C at low to intermediate pressures, involving the minerals amphibole, chlorite, anorthite, clinozoisite, dolomite, chloritoid, garnet, margarite, andalusite, and calcite. By solving independent sets of non-linear equations formed from equilibrium relationships, we calculate not only the loci of reactions in pressuretemperature-x(CO2) space, but also the compositions of coexisting minerals in terms of the substitutions, FeMg-1 and (Fe,Mg)SiAl-1Al-1. Invariant, univariant and divariant equilibria are calculated and discussed in relation to naturally-occurring greenschist facies metabasic and siliceous dolomitic mineral assemblages. We thus avoid the use of activity-corrected curves so commonly presented in the literature as a substitute for genuine univariant phase diagram boundaries.  相似文献   

18.
Equilibria involving acmite, albite, nepheline, quartz, anda liquid phase constitute the petrologically important partof the system Na2O–Al2O3–Fe2O2–SiO2, and theunivariant and invariant relations provide useful analogiesfor a wide variety of alkaline igneous rocks. These relationsare dominated by the incongruent melting behaviour of acmite,which does not appear on the liquidus of the join acmite-nepheline-silica;instead, a broad field of hematite is present and acmite crystallizesonly from liquids containing potential sodium silicate. Consequently,the oversaturated and undersaturated eutectics, correspondingto granitic and nepheline syenitic liquids, are rich in sodiumsilicate and distinct from those found in Petrogeny's Residuasystem: the temperatures of the eutectics are 7285C and 7155C, respectively. Survival of peralkaline granite in the aluminouscontinental crust can be explained by the strongly peralkalinecomposition of the oversaturated eutectic. Magma of this typemay be the primitive granite of the non-orogenic zones. Theubiquitous alkali metasomatism around alkaline complexes canalso be interpreted in terms of residual liquids enriched inalkali silicates. Transition from undersaturated to oversaturatedliquids is possible by fractionation of hematite and a new processfor achieving the reverse transition has been found. This dependson the substitution of Fe3 for Al3 in feldspar and suggestsa more important role for syenite in any scheme of petrogenesis. Each of the two eutectics is linked to a corresponding peritecticat which hematite reacts to give acmite. The liquid at the undersaturated,quaternary reaction point is of ijolitic type, providing thefirst intimation that ijolite may represent a low-melting fractionin nature. The system Na2O–Al2O3–Fe2O3–SiO2thus constitutes the peralkaline residua system and on thisbasis a coherent picture of stable continental magmatism canbe constructed. Ijolite is seen as the low-melting fractionfrom a range of peralkaline compositions and from rocks suchas melilite basalt, while the frequently associated carbonatiteis considered to be the volatile-rich, fugitive material fromthe mantle. Such a relationship is consistent with the dualassociation of carbonatite with either ijolite or kimberliteunder different tectonic conditions. The more common syenite,nepheline syenite, and alkaline granite of the non-orogenicregions are regarded as low-melting fractions from basalticmaterials in the deep crust. Most of this activity, involvingmagmas of residual type, could thus be explained in terms ofpartial melting in the deep crust and upper mantle. A possiblemechanism for this would be arching of the rigid continentalcrust, the consequent relief of lithostatic load giving riseto melting, and the concentration of fugitive constituents,in the underlying zones.  相似文献   

19.
Using an internally consistent thermodynamic dataset and updatedmodels of activity–composition relation for solid solutions,petrogenetic grids in the system NKFMASH (Na2O–K2O–FeO–MgO–Al2O3–SiO2–H2O)and the subsystems NKMASH and NKFASH have been calculated withthe software THERMOCALC 3.1 in the PT range 5–36kbar and 400–810°C, involving garnet, chloritoid,biotite, carpholite, talc, chlorite, kyanite/sillimanite, staurolite,phengite, paragonite, albite, glaucophane, jadeite, with quartz/coesiteand H2O in excess. These grids, together with calculated AFMcompatibility diagrams and PT pseudosections, are shownto be powerful tools for delineating the phase equilibria andPT conditions of Na-bearing pelitic assemblages for avariety of bulk compositions from high-P terranes around theworld. These calculated equilibria are in good agreement withpetrological studies. Moreover, contours of the calculated phengiteSi isopleths in PT pseudosections for different bulkcompositions confirm that phengite barometry is highly dependenton mineral assemblage. KEY WORDS: phase relations; HP metapelite; NKFMASH; THERMOCALC; phengite geobarometry  相似文献   

20.
Phase equilibrium data have been collected for isobaricallyunivariant melting of simplified Iherzolite compositions inthe system CaO-MgO-Al2O3 SiO2-Na2O over a pressure range of7–35 kbar. These data permit the melting behavior of awide variety of model lherzolite compositions to be determinedquantitatively by algebraic methods. Two P-T univariant meltingreactions, corresponding to plagioclase to spinel lherzoliteand spinel to garnet lherzolite, are identified as peritectic-typetransitions and have positive Clapeyron slopes. The univariantcurves move to higher pressures and temperatures with increasingNa2O in the liquid. The effect of the univariant curves on meltingis to produce low-temperature regions and isobarically invariantmelting intervals along lherzolite solidi. In the plagioclaselherzolite stability field, melting of four-phase model lherzoliteis pseudo-invariant, occurring over small temperature intervals(5C) and producing liquids that are quartz tholeiites at <8kbar and olivine tholeiites at >8 kbar. Calculated equilibriumconstants for plagioclase-liquid equilibria show both temperatureand pressure dependence. Plagioclase with anorthite content(AN) >90 mol%, as observed in some oceanic basalts, can crystallizefrom liquids with <1% Na2O. Melting of spinel lherzoliteis not pseudo-invariant but occurs over large temperature intervals(15–60 C), producing a wide range in liquid compositions,from alkali basalts and alkali picrites at low to moderate degreesof melting (<1–10%) to olivine tholeiites and picritesat higher degrees of melting (>10%). On the basis of limiteddata in the garnet Iherzolite field, melts from garnet lherzoliteare more silica rich for a given degree of melting than meltsfrom spinel lherzolite, and liquid compositions trend towardenstatite with increase in pressure. Source fertility (especiallyNa2O content) has a strong control on the temperature of meltingand liquid composition. Less fertile sources produce smalleramounts of liquids richer in normative silica. For certain bulkcompositions (high SiO2 and low Al2O3), spinel is not a stablephase along the lherzolite solidus.  相似文献   

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