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1.
Recent experimental studies have shown that the rates of Al–Si order-disorder and interdiffusion in alkali feldspars at high pressures under dry conditions increase dramatically in the approximate pressure range 7–14 kb, depending on temperature and feldspar composition (Goldsmith 1987, 1988). Enhancement of Al–Si interdiffusion rates is ascribed to the involvement of hydrogen, but the species of hydrogen involved is undetermined.A simple kinetic analysis of the data of Goldsmith (1987) on disordering of dry albite at 800°–950° C and 6–24 kb in the solid media press is consistent with the NaCl pressure cell acting as a proton donor by enhancing dissociation of water in the pressure medium, generating a high in the experimental environment. The rate constant for disordering of albite is found to increase linearly with the estimated experimental and with the density of aqueous salt solution, implicating H+ as the rate-enhancing species.Further experimental studies confirm the importance of . At 16 kb and 850° C, dry albite in sealed Pt capsules in a NaCl cell containing tantalum powder (which reduces H2O to H2) remains highly ordered over the same time that complete disordering would occur in the absence of Ta. H2 cannot therefore be the rate-enhancing species. At 1 kb and 850° C, the extent of Al–Si disorder in albite in direct contact with various NaCl–H2O solutions increases from partially disordered for pure H2O to completely disordered for saturated aqueous NaCl solution, giving strong support to the proton model. SIMS scanning ion imaging of albite run products demonstrates conclusively that solution-reprecipitation is not responsible for enhanced disordering rates.Results of disordering experiments in the solid media apparatus cannot be duplicated in Ar gas media internally-heated pressure vessels, even with the same experimental configuration around the albite-bearing capsules, due to the different proton-buffering capacities of the solid and gas media apparatus.  相似文献   

2.
The inability to synthesize pure tschermakite over the range of 6–15 kbar and 700–850° C, the optimal conditions reported by Oba (1978), prompted a reinvestigation of the join tremolite-tschermakite which was originally investigated by Jasmund and Schäfer (1972). The results of syntheses performed in 10 mol% increments along this join at 12 kbar and 850° C indicate that solid solution exists only in the composition range or TS0TR100 to TS50 TR50. This was confirmed by direct chemical analyses of the synthetic amphiboles and by monitoring the shift in the d310. Syntheses along this same join at 3 kbar and 850° C reveal an even more limited range of solid solution, namely from TS0TR100 to TS10TR90, which was also confirmed by direct analyses and variation in the d310 values. Comparison of the results at 3 kbar and 12 kbar indicates a pressure dependency of Al solubility in tremolite corresponding to 0.17 Al (total)/kbar on the basis of 23 oxygens. An attempt to re-equilibrate tremolite and an Al-rich amphibole at 6 kbar and 850° C to an intermediate composition resulted in the Al-rich amphibole displaying the best evidence of re-equilibration, which was to a lower Al content. This observation supports the results obtained from the synthesis experiments by showing that decreased pressure decreases the Al solubility. It is emphasized that the Al content of natural calcic amphiboles, whose compositions are approximately modeled by the join tremolite-pargasite, is probably a function of both pressure and temperature and must ultimately be calibrated in a fashion analogous to the pyroxenes.  相似文献   

3.
The concentrations of Na, Al, and Si in an aqueous fluid in equilibrium with natural albite, paragonite, and quartz have been measured between 350°C and 500°C and 1 to 2.5 kbar. Si is the dominant solute in solution and is near values reported for quartz solubility in pure H2O. At 1 kbar the concentrations of Na and Al remain fairly constant from 350°C to 425°C but then decrease at 450°C. At 2 kbar, Na increases slightly with increasing temperature while Al remains nearly constant. Concentrations of Si, Na, and Al all increase with increasing pressure at constant temperature.The molality of Al is close to that of Na and is nearly a log unit greater than calculated molalities assuming Al(OH)03 is the dominant Al species. This indicates a Na-Al complex is the dominant Al species in solution as shown by Anderson and Burnham (1983) at higher temperature and pressure. The complex can be written as NaAl(OH)04 ± nSiO2 where n is the number of Si atoms in the complex. The value of n is not well constrained but appears to be less than or equal to 3.The results indicate Al can be readily transported in pure H2O solutions at temperatures and pressures as low as 350°C and 1 kbar.  相似文献   

4.
Large discrepancies are reported for the near-solidus, pressure-temperature location of the spinel to garnet lherzolite univariant curve in the system CaO-MgO-Al2O3-SiO2 (CMAS). Experimental data obtained previously from the piston-cylinder apparatus indicate interlaboratory pressure differences of up to 30% relative. To investigate this disparity—and because this reaction is pivotal for understanding upper mantle petrology—the phase boundary was located by means of an independent method. The reaction was studied via in situ X-ray diffraction techniques in a 6-8 type multianvil press. Pressure is determined by using MgO as an internal standard and is calculated from measured unit cell volume by using a newly developed high-temperature equation of state for MgO. Combinations of real-time and quenched-sample observations are used to bracket the phase transition. The transition between 1350 and 1500°C was reversed, and the reaction was further constrained from 1207 to 1545°C. Within this temperature range, the transition has an average dT/dP slope of ∼40 ± 10°C/kbar, consistent with several previous piston-cylinder studies. Extrapolation of our curve to 1575°C, an established temperature of the P-T invariant point, yields a pressure of 25.1 ± 1.2 kbar. We also obtained a real-time reversal of the quartz-coesite transition at 30.5 ± 2.3 kbar at 1357°C, which is about 2 to 4 kbar lower in pressure than previously determined in the piston-cylinder apparatus.  相似文献   

5.
Staurolite and corundum are found as inclusions in tourmaline in a talc-phlogopite-chlorite-albite chist near Mount Bernstein (71°37S, 163°07E), northern Victoria Land, Antarctica. These inclusions are interpreted as relics of a staurolite-talc-corundum-chlorite assemblage that was stable during an early stage in the metamorphic cycle and subsequently armored by tourmaline, probably during the middle stage. Pressures and temperatures during the middle stage are estimated to be 650–700°C and 5.5–6.4 kbar. The transition from the early to the middle stage represents a roughly isothermal decrease in pressure of 2–3 kbar. During a late retrograde stage (T=300–370°C, P=3–5 kbar), staurolite was partly replaced by a muscovitic aggregate containing clinozoisite, pumpellyite, and margarite.The staurolite is unusually Si-poor (26.77, 25.85 weight % SiO2 or 7.275, 7.091 Si per formula unit for 46 oxygens anhydrous), Al-rich (58.00, 57.85% Al2O3, 18.579, 18.702 Al), low in divalent cations (Fe+Mg+Mn+Zn=3.301, 3.560) and magnesian (atomic Mg/(Mg+Fe)=0.42, 0.40). Ion microprobe analysis of the first grain indicates about 0.2% Li2O (0.219 Li) is present. The following substitutions are proposed to explain the unusual chemistry of this staurolite (crystallographic site notation of Smith 1968, in bold letters): Al(Si)+Al(Al(3A,B))Si(Si)+Fe(Fe), Li(Fe)+Al(Al(3A,B))2 Fe(Fe), and 2 Al(Al(3A,B)) 3 Fe(Fe).According to a pressure-temperature diagram constructed by the method of Schreinemakers for the model system FeO-MgO-Al2O3-SiO2 (H2O in excess), the talc-staurolite assemblage should be stable only in quartz-free rocks at temperatures near 700° C and pressures of 8 kbar or more. The rarity of the staurolite-talc assemblage even in Mg-Al-rich rocks metamorphosed at the appropriate pressure-temperature conditions is attributed to the appearance of anthophyllite or, in Na2O-bearing rocks, gedrite. Orthoamphibole-cordierite and orthoamphibolekyanite assemblages with chlorite or corundum are incompatible with staurolite-talc±albite. In rocks lacking corundum and formed at pressures above the stability limit of cordierite, staurolite-talc may be metastable relative to orthoamphibole-kyanite, while in corundum-bearing rocks, staurolite-talc may appear under certain conditions, possibly at higher water activities than the orthoamphibole-kyanite assemblage.  相似文献   

6.
Estimation of metamorphic pressures in low temperature eclogite (Type C) is difficult because of the high variance mineral assemblages and problems in geothermometry, solution properties of low-temperature omphacite, and the thermodynamic properties of clinozoisite. We have considered equilibria in the CaO–FeO–MgO–TiO2–Al2O3–SiO2–H2O (CFMTASH) system involving the phase components, quartz, rutile, kyanite, ilmenite, almandine, pyrope, grossular, clinozoisite, sphene, diopside, and H2O-fluid There are four linearly independent equilibria involving the phase components in this system. Because kyanite can crystallize as a nearly pure phase, the lack of kyanite in a rock indicates that a Al2SiO5 is<1.0. If we can estimate temperature independently, we can solve for a Al2SiO5 and pressure by using two of the equilibria in isothermal pressure-activity diagrams. We have applied this approach to eclogites from New Caledonia and from southwestern Oregon. For the New Caledonia eclogites, calculated pressures range from 11.2 to 13.6 kbar at 500°C, and are consistent with the minimum pressures based upon the presence of jadeitic pyroxene+quartz and the lack of stable albite. Oregon eclogites come from different tectonic blocks and calculated minimum pressures of 11–12 kbar are based upon the presence of jadeitic pyroxene+rutile+garnet and lack of stable albite and ilmenite at reduced values of a SiO2 (0.7–0.9).  相似文献   

7.
Corundum (α-Al2O3) solubility was measured in 0.1-molal CaCl2 solutions from 400 to 600°C between 0.6 and 2.0 kbar. The Al molality at 2 kbar increases from 3.1 × 10−4 at 400°C to 12.7 × 10−4 at 600°C. At 1 kbar, the solubility increases from 1.5 × 10−4m at 400°C to 3.4 × 10−4m at 600°C. These molalities are somewhat less than corundum solubility in pure H2O (Walther, 1997) at 400°C but somewhat greater at 600°C. The distribution of species was computed considering the Al species Al(OH)30 and Al(OH)4−, consistent with the solubility of corundum in pure H2O of Walther (1997) and association constants reported in the literature. The calculated solubility was greater than that measured except at 600°C and 2.0 kbar, indicating that neutral-charged species interactions are probably important.A Setchénow model for neutral species resulted in poor fitting of the measured values at 1.0 kbar. This suggests that Al(OH)30 has a greater stability relative to Al(OH)4− than given by the models of Pokrovskii and Helgeson (1995) or Diakonov et al. (1996). The significantly lower Al molalities in CaCl2 relative to those in NaCl solutions at the same concentration confirm the suggestions of Walther (2001) and others that NaAl(OH)40 rather than an Al-Cl complex must be significant in supercritical NaCl solutions to give the observed increase in corundum solubility with increasing NaCl concentrations.  相似文献   

8.
 The melting reaction: albite(solid)+ H2O(fluid) =albite-H2O(melt) has been determined in the presence of H2O–NaCl fluids at 5 and 9.2 kbar, and results compared with those obtained in presence of H2O–CO2 fluids. To a good approximation, albite melts congruently at 9 kbar, indicating that the melting temperature at constant pressure is principally determined by water activity. At 5 kbar, the temperature (T)- mole fraction (X (H2O) ) melting relations in the two systems are almost coincident. By contrast, H2O–NaCl mixing at 9 kbar is quite non-ideal; albite melts ∼70 °C higher in H2O–NaCl brines than in H2O–CO2 fluids for X (H2O) =0.8 and ∼100 °C higher for X (H2O) =0.5. The melting temperature of albite in H2O–NaCl fluids of X (H2O)=0.8 is ∼100 °C higher than in pure water. The P–T curves for albite melting at constant H2O–NaCl show a temperature minimum at about 5 kbar. Water activities in H2O–NaCl fluids calculated from these results, from new experimental data on the dehydration of brucite in presence of H2O–NaCl fluid at 9 kbar, and from previously published experimental data, indicate a large decrease with increasing fluid pressure at pressures up to 10 kbar. Aqueous brines with dissolved chloride salt contents comparable to those of real crustal fluids provide a mechanism for reducing water activities, buffering and limiting crustal melting, and generating anhydrous mineral assemblages during deep crustal metamorphism in the granulite facies and in subduction-related metamorphism. Low water activity in high pressure-temperature metamorphic mineral assemblages is not necessarily a criterion of fluid absence or melting, but may be due to the presence of low a (H2O) brines. Received: 17 March 1995/Accepted: 9 April 1996  相似文献   

9.
The reaction fayalite+anorthite=garnet (GAF) has been investigated in a piston-cylinder apparatus and in an internally heated gas apparatus. Piston-cylinder reversals were obtained at 900 °C (6.0–6.4 kbar), 950 °C (6.3–6.8 kbar), 1000 °C (6.6–7.1 kbar), and 1050 °C (7.0–7.3 kbar). Gas-apparatus experiments yielded a reversal at 7 kbar (993–1049 °C). Results are consistent with earlier experimental studies. Unless garnet Ca–Fe mixing is attended by an excess entropy of at least 2–3 J/K-atom, discrepancies remain between calculated and experimentally determined slopes for GAF. The discrepancy is greater if there is no Al–Si disorder in anorthite. High temperature thermodynamic data for almandine and grossular are needed to help resolve this problem.  相似文献   

10.
The solubility of calcite in NaCl-H2O and in HCl-H2O fluids was measured using an extraction-quench hydrothermal apparatus. Experiments were conducted at 2 kbar, between 400° C and 600° C. Measurements in NaCl-H2O were conducted in two ways: 1) at constant pressure and NaCl concentration, as a function of temperature; and 2) at constant pressure and temperature, as a function of NaCl concentration. In both the NaCl-H2O and the HCl-H2O systems, the solubility of calcite increases with increasing chlorine concentrations. For example, the log calcium molality in equilibrium with calcite increases from –3.75 at 2 kbar and 500° C, in pure H2O to –3.10 at 2 kbar and 500° C at log NaCl molality=–1.67. At fixed pressure and NaCl molality, the solubility of calcite is almost constant from 400° C to 550° C, but increases somewhat at higher temperatures. The results can be used to determine the dominant calcium species in the experimental solutions as a function of NaCl concentration and to obtain values for the second dissociation constant of CaCl2(aq). At 2 kbar, 400° C, 500° C, and 600° C, we calculate values for the log of the dissociation constant of CaCl+ of –2.1, –3.2, and –4.3, respectively. The 400° C and 500° C values are consistent with those obtained by Frantz and Marshall (1982) using electrical conductance techniques. However, our 600° C value is 0.8 log units higher than that reported by Frantz and Marshall. The calcite solubilities in the NaCl-H2O and HCl-H2O systems are inconsistent with the solubilities of calcite in pure H2O reported by Walther and Long (1986). They are, however, consistent with the measurements of calcite solubilities in pure H2O presented in this study. These results allow for the calculation of the solubilities of calcium silicates and carbonates in fluids that contain CO2 and NaCl.  相似文献   

11.
Fluid-solid-solid dihedral angles in the NaCl-H2O-CO2-calcite-dolomite-magnesite system have been determined at pressures ranging from 0.5 to 7 kbar and temperatures from 450°C to 750°C. At 1 kbar and 650°C, both dolomite and magnesite exhibit a dihedral angle minimum for intermediate H2O-CO2 fluids similar to that previously determined by the present authors for calcite, but the depth of the minimum is smaller, being above the critical value of 60° for both dolomite and magnesite for all fluid compositions. Calcite-calcite-brine dihedral angles at 650°C have been determined in the pressure range 1–5 kbar. Angles decrease with increasing salt content of the fluid, tending towards a constant value of about 65° for strong brines at pressures above 2 kbar. There is a general increase of angle with increasing pressure which is most marked for strong brines. A positive correlation of angle with pressure is also observed in calcite-H2O-CO2 fluids, the position of the minimum moving towards higher angles and towards H2O-rich fluids with increasing pressure. The permeability window previously observed by the present authors at 1 kbar and intermediate fluid compositions closes at about 1.5 kbar. The results demonstrate that the permeability of carbonates to grain edge fluid flow is only possible at low pressures and for fluids of restricted H2O-CO2-NaCl compositions. However, geochemical evidence from metamorphic terrains suggests that pervasive infiltration does occur under conditions where impermeability is predicted. From examination of published studies of infiltrated carbonates we conclude that deformation plays a critical role in enhancing carbonate permeability. Possible mechanisms for this include shear-enhanced dilatancy (micro-cracking), fluid inclusion drag by deformation-controlled grain boundary migration, and dynamically maintained transient grain boundary fluid films.  相似文献   

12.
In the system CaO-MgO-A12O3-SiO2 the tie lines connecting anorthite with other phases are sequentially broken down with increasing pressure according to the following univariant reactions: anorthite+ enstatitess+sillimanite pyrope-grossularss+quartz (3), anorthite+enstatitess pyrope-grossularss+diopsidess+quartz (2), anorthite+pyrope-grossularss+ quartz diopsidess+kyanite (4) and anorthite+diopsidess grossular-pyropess +kyanite+quartz (8). At 1,200 ° C these reactions occur at 14.5± 0.5, 15.5±0.5, 19.5±0.5 and 26.4±1 kilobar and have positive slopes (dP/dT) of 1±0.5, 2.8±0.5, 13.3±0.5 and 24±2bars/°C respectively. An invariant point involving kyanite rather than sillimanite, occurs at 850 °C±25 °C and 14.5±0.5kbar at the intersection of reactions (3), (2) and (4). Reaction(4) exhibits significant curvature with an increase in dP/dT from 13.3±0.5 to 18.5± 0.5 bars/°C between 1,050° and 850° C. The pressure at which the complete grossular-pyrope join is stable with quartz is estimated at 41 ± 1 kbar at 1,200 ° C. The pressure at which garnet appears according to reaction (2) is lowered by 5 kbar for a composition with anorthite and orthopyroxene (En0.5Fs0.5). Enstatite and plagioclase (An0.5Ab0.5) first produce garnet at 2 kbar higher pressure than enstatite and pure anorthite (reaction (2)). The calcium content of garnet in various divariant assemblages is relatively insensitive to temperature but very sensitive to pressure, it is therefore a useful geobarometer. At metamorphic temperatures of 700–850 °C pressures of 8–10 kbar are required for the formation of quartz-bearing garnet granulites containing calcic plagioclase and with (Mg/Mg+Fe) bulk = 0.5.  相似文献   

13.
Experiments with synthetic starting materials of muscovite, phlogopite, zoisite, kyanite and quartz were performed in the pressure temperature range 10–25 kbar, 640–780° C under water excess conditions. The reaction muscovite+zoisite+quartz+vapor=liquid+kyanite was bracketed at 10.5 kbar/689–700° C, 15.5 kbar/709–731° C and 20 kbar/734–745° C. The equivalent reaction in the Mg-bearing system muscovitess +zoisite+quartz+vapor=liquid+kyanite+phlogopitess lies at the same temperature around 10 kbar and approximately 10° C higher around 20 kbar, compared with the Mg-free reaction. At slightly higher temperatures formation of melt and tremolitess was reversibly observed from the assemblage phlogopitess+zoisite +kyanite+quartz around 10.5 kbar/690–710° C, 15.5 kbar/720–750° C and 20.5 kbar/745–760° C. In the subsolidus region, the reaction muscovitess+talcss+ tremolitess=phlogopitess+zoisite+quartz+vapor were located in the range 700° C/16.7–19.0 kbar and 740° C/19.7–20.8 kbar. From these data, a wedge shaped stability field of phlogopitess+zoisite+quartz appears with a high P, T termination around 21 kbar/755° C. Muscovite+tremolite+talc or kyanite comes in at higher pressures. These phase relations are in qualitative accord with petrographic observations from high pressure metamorphic areas. Formation and crystallization of melts in rocks of a wide compositional range involving zoisite/epidote has been ascribed to relatively high pressures and is consistent with experimentally determined stability fields in the simplified KCMASH system.  相似文献   

14.
Dumortierite, generally simplified as Al7BSi3O18, was synthesized in the pure system Al2O3–B2O3–SiO2–H2O (ABSH) using gels with variable Al/Si ratios mixed with H3BO3 and H2O in known proportions as starting materials. Synthesis conditions ranged from 3 to 5 and 15 to 20 kbar fluid pressure at 650° to 880°C. On the basis of analyses, synthetic dumortierite shows relatively narrow homogeneity ranges with regard to Al/Si which, however, vary as a function of pressure: at low pressures (3–5 kbar) Al/Si is 2.77–2.94 versus 2.33–2.55 at high pressures (15–20 kbar). Outside of these homogeneity limits, dumortierite was found to coexist with quartz or corundum, depending on the starting composition. Whereas synthetic dumortierite invaribly contains 1.0 boron atom per formula unit (p.f.u.) based on 18 oxygens, the water contents vary drastically as a function of pressure and temperature (1.32–2.30 wt.% H2O or 0.85–1.47 H p.f.u.). H2O is an essential component in dumortierite. Structural formulae based on complete chemical analyses of the dumortierites synthesized reveal that there is invariably an Si-deficiency against the ideal number of 3.0 p.f.u. In the calculation procedure used here, this deficiency is balanced by assuming tetrahedral Al. The remaining Al, taken to occupy the octahedral sites, is always below the ideal number of 7.0 p.f.u. Charge-balancing the structure with the hydrogen found analytically leads to two different mechanisms of H incorporation: (1) 3H+ + octahedral vacancy for Al[6]; (2) H+ + tetrahedral Al for Si[4]. Dumortierite synthesized at high fluid pressure contains little Al[4] and, thus, little H+ of type 2; its hydrogen is predominantly present as type 1. Conversely, dumortierite formed at low fluid pressures is high in Al[4] and hydrogen type 2. The amounts of hydrogen type 1 in low-pressure dumortierites decrease with rising temperatures of synthesis. Typical structural formulae are: (Al6.670.33)[Al0.49Si2.51–O13.53(OH)1.47](BO3) for a low-pressure product, and (Al6.680.32)[Al0.09Si2.91O13.94(OH)1.06](BO3) for a high-pressure product. Independently of the synthesis conditions, dumortierite was found always to be orthorhombic, with b0/a0 deviating slightly, but significantly from the valid for hexagonal lattice geometry. As a function of increasing Al/Si in the synthetic crystals, their a0, c0, and V0 rise, whereas b0 decreases. Thus b0/a0 decreases most sensitively with rising Al/Si and also with growing Al[4]. More experimentation is required before the compositional variations of dumortierite found here can be applied successfully to geothermobarometry of natural rocks.  相似文献   

15.
The solubilities of the assemblages albite + paragonite + quartz and jadeite + paragonite + quartz in H2O were determined at 500 and 600 °C, 1.0-2.25 GPa, using hydrothermal piston-cylinder methods. The three minerals are isobarically and isothermally invariant in the presence of H2O, so fluid composition is uniquely determined at each pressure and temperature. A phase-bracketing approach was used to achieve accurate solubility determinations. Albite + quartz and jadeite + quartz dissolve incongruently in H2O, yielding residual paragonite which could not be retrieved and weighed. Solution composition fixed by the three-mineral assemblage at a given pressure and temperature was therefore bracketed by adding NaSi3O6.5 glass in successive experiments, until no paragonite was observed in run products. Solubilities derived from experiments bounding the appearance of paragonite thus constrain the equilibrium fluid composition. Results indicate that, at a given pressure, Na, Al, and Si concentrations are higher at 600 °C than at 500 °C. At both 500 and 600 °C, solubilities of all three elements increase with pressure in the albite stability field, to a maximum at the jadeite-albite-quartz equilibrium. In the jadeite stability field, element concentrations decline with continued pressure increase. At the solubility maximum, Na, Al, and Si concentrations are, respectively, 0.16, 0.05, and 0.48 molal at 500 °C, and 0.45, 0.27, and 1.56 molal at 600 °C. Bulk solubilities are 3.3 and 10.3 wt% oxides, respectively. Observed element concentrations are everywhere greater than those predicted from extrapolated thermodynamic data for simple ions, monomers, ion pairs, and the silica dimer. The measurements therefore require the presence of additional, polymerized Na-Al-Si-bearing species in the solutions. The excess solubility is >50% at all conditions, indicating that polymeric structures are the predominant solutes in the P-T region studied. The solubility patterns likely arise from combination of the large solid volume change associated with the albite-jadeite-quartz equilibrium and the rise in Na-Al-Si polymerization with approach to the hydrothermal melting curves of albite + quartz and jadeite + quartz. Our results indicate that polymerization of Na-Al-Si solutes is a fundamental aspect of fluid-rock interaction at high pressure. In addition, the data suggest that high-pressure metamorphic isograds can impose unexpected controls on metasomatic mass transfer, that significant metasomatic mass transfer prior to melting should be considered in migmatitic terranes, and that polymeric complexes may be an important transport agent in subduction zones.  相似文献   

16.
The pressure of the reaction albite=jadeite and quartz was measured at 600° C by workers in six geophysical laboratories for the purpose of comparing pressure calibration procedures for the solid-pressure piston-cylinder apparatus. All groups used the same starting mix of crystalline reactant and products and all obtained hydrothermal reversals of the equilibrium. Solid pressure media used included talc, NaCl, boron nitride, pyrophyllite, pyrex glass and crushable ceramic. Various means of calibration were used, including internal standardization by transitions in indicator substances and the piston-in, piston-out bracketing method.There was agreement among all groups—the average preferred value of 16.3 kilobars at 600° C is enclosed by all of the error brackets assigned by the various investigators. This average preferred value is lower by nearly two kilobars than the often-quoted extrapolation of Birch and LeComte's data (1960). It will be important for both petrology and high-pressure technology to test this result in a very high gas pressure apparatus.  相似文献   

17.
The univariant high-pressure reaction of aluminous enstatite and spinel to pyrope and forsterite in the MgO-Al2O3-SiO2 system has been determined in the temperature range 900 °–1100 °C by hydrothermal reversals in the piston-cylinder apparatus using the low-friction NaCl pressure medium. A mixture of synthetic minerals, including an enstatite with 6 wt% Al2O3, with product and reactant assemblages in nearly equal amounts, was the starting material. The equilibrium pressure of 19.3±0.3 kbar at 1000 ° C and average dP/dT slope of 8.0 bars/ ° C confirm the strong curvature of the equilibrium below 1200 ° C deduced by Obata (1976) from a theoretical study of experimental Al2O3 isopleths of enstatite in the garnet field. His prediction of an absolute minimum pressure near 18 kbar of the garnet peridotite assemblage in the ternary system is undoubtedly correct.Three reversed determinations of the equilibrium Al2O3 content of enstatite in the presence of spinel +forsterite were made at points adjacent to the univariant curve. The points are 5.5 wt% Al2O3 at 950 ° C and 20 kbar, 6.2 wt% at 1000 ° C and 20 kbar and 7.2 wt% at 1080 ° C and 20 kbar. These values are somewhat higher than given by the MacGregor (1974) isopleth set and quite close to those predicted by Fujii (1976) from experimental synthesis data at higher temperatures, using the Wood and Banno (1973) model of ideal solution of the Mg2Si2O6 and MgAl2SiO6 components in enstatite to reduce the data.All of the available spinel-field isopleth data can be systematized with the use of the ideal solution model. A value of H 0 of 9000 cal fits the reduced data well, and is in agreement with the calorimetrically determined value of 8500±1900 calories. An accurate calculation of the dP/dT slope of the univariant equilibrium at 1000 ° C based on calorimetry gives 7±2bars/ °C, also in good agreement with experiment. Thus, all of the available experimental and calorimetric data are consistent with the ideal-solution aluminous enstatite model.The dP/dT slopes of the spinel-field isopleths are too large to permit their use as an accurate geobarometric scale. They do have considerable potential as a thermometric indicator for certain natural peridotites, however. The southwestern Oregon overthrust peridotite masses of Cretaceous age have enstatite of 5.6 wt% Al2O3 with spinel of nearly 80 mole% MgAl2O4. The present reduced isopleth data directly give 930 ° C for the equilibration, assuming 12 kbar pressure. A first order correction based on ideal solution departures from the ternary system, as suggested by Stroh (1976) gives 1000 ° C. Thus, the high temperatures deduced by Medaris (1972) are confirmed. The pressure cannot be deduced independently from the pyroxene Al2O3 contents.  相似文献   

18.
To further our knowledge of the effects of volatile components on phase relationships in aluminosilicate systems, we determined the vapor saturated solidi of albite, anorthite, and sanidine in the presence of CO2 vapor. The depression of the temperature of the solidus of albite by CO2 decreases from 30° C at 10 kbar, to 10° C at 20 kbar, to about 0 at 25 kbar, suggesting that the solubility of CO2 in NaAlSi3O8 liquid in equilibrium with solid albite decreases with increasing pressure and temperature. In contrast, CO2 lowers the temperature of the solidus of anorthite by 30° C at 14 kbar, and by 70dg C at 25 kbar. This contrasting behavior of albite and anorthite is also reflected in the behavior of melting in the absence of volatile components. Whereas albite melts congruently to a liquid of NaAl-Si3O8 composition to pressures of 35 kbar, anorthite melts congruently to only about 10 kbar and, at higher pressures, incongruently to corundum plus a liquid that is enriched in SiO2 and CaO and depleted in Al2O3 relative to CaAl2Si2O8.The tendency toward incongruent melting with increasing pressure in albite and anorthite produces an increase in the activity of SiO2 component in the liquid ( ). We predict that this increases the ratio of molecular CO2/CO 3 2– in these liquids, but the experimental results from other workers are mutually contradictory. Because of the positive dP/dT of the albite solidus and the negative dP/dT of the anorthite solidus, we propose that a negative temperature derivative of the solubility of molecular CO2 in plagioclase liquids may partly explain the decrease in solubility of carbon with increasing pressure in near-solidus NaAlSi3O8 liquids, which is in contrast to that in CaAl2Si2O8 liquid. Also, reaction of CO2 with NaAlSi3O8 liquid to form CO 3 2– that is complexed with Na+ must be accompanied by a change in Al3+ from network-former to network-modifier, as Na+ is no longer abailable to charge-balance Al3+ in a network-forming role. However, when anorthite melts incongruently to corundum plus a CaO-rich liquid, the complexing of CO 3 2– with the excess Ca2+ in the liquid does not require a change in the structural role of aluminum, and it may be more energetically favorable.The depression of the temperature of the solidus of sanidine resulting from the addition of CO2 increases from 50° C at 5 kbar to 170° C at 15 kbar. In marked contrast to the plagioclase feldspars, sanidine melts incongruently to leucite plus a SiO2-rich liquid up to the singular point at 15 kbar. Above this pressure, sanidine melts congruently, resulting in a decrease in the with increasing pressure in the interval up to 15 kbar. Above this pressure, the congruent melting of sanidine results in a lower and nearly constant relative to those of albite and anorthite, and CO2 produces a nearly constant freezing-point depression of about 170° C. Because of the low at pressures above the singular point, we infer that most of the carbon dissolves as CO 3 2– , resulting in a low CO2/ CO 3 2– , but a high total carbon content.The principles derived from the studies of phase equilibria in these chemically simple systems provide some information on the structural and thermal properties of magmas. We propose that the is an important parameter in controlling the speciation of carbon in these feldspathic liquids, but it certainly is not the only factor, and it may be relatively less significant in more complex compositions. In addition, our phase-equilibria approach does not provide direct thermal and structural information as do calorimetry and spectroscopy, but the latter have been used primarily on glasses (quenched liquids) and cannot be used in situ to derive direct information on liquids at elevated pressures, as can our method. Hopefully, the results of all of these approaches can be integrated to yield useful results.Institute of Geophysics and Planetary Physics, Contribution No. 2744  相似文献   

19.
A Permo-Triassic pelite-carbonate rock series (with interacalated metabasitic rocks) in the Cordilleras Béticas, Spain, was metamorphosed during the Alpine metamorphism at high pressures (P min near 18 kbar). The rocks show well preserved sedimentary features of evaporites such as pseudomorphs of talc, of kyanite-phengitetalc-biotite, and of quartz after sulfate minerals, and relicts of baryte, anhydrite, NaCl, and KCl, indicating a salt-clay mixture of illite, chlorite, talc, and halite as the original rock. The evaporitic metapelites have a whole rock composition characterized by high Mg/(Mg+Ca) ratios>0.7, variable alkaline and Sr, Ba, contents, but are mostly K2O rich (<8.8 wt%). The F (<2600 ppm), Cl (<3600 ppm), and P2O5 (<0.24 wt%) contents are also high. The pelitic member of this series is a fine grained biotite rock. Kyanite-phengite-talc-biotite aggregates in pseudomorphs developed in the high pressure stage. Albite-rich plagioclase was formed when the rocks crossed the albite stability curve in the early stages of the uplift. Scapolite, rich in NaCl (Ca/(Ca+Na) mol% 24–40) and poor in SO4, with Cl/(Cl+CO3) ratios between 0.6 and 0.8, formed as porphyroblasts, sometimes replacing up to 60% of the rock in a late stage of metamorphism (between 10 and 5 kbar, near 600°C). No reaction with albite is observed, and the scapolite formed from biotite by: $$\begin{gathered} Al - biotite + CaCO_3 + NaCl + SiO_2 \hfill \\ = Al - poor biotite + scapolite + MgCO_3 + KCl \hfill \\ + MgCl_2 + H_2 O \hfill \\ \end{gathered}$$ Calculated fluid composition in equilibrium with scapolite indicates varying salt concentrations in the fluid. Distribution of Cl and F in biotite and apatite also indicates varying fluid compositions.  相似文献   

20.
Green and Vernon (1974) have experimentally determined a divariant field of cordierite-orthoamphibole-kyanite-quartz with a slope of 12±4 bars per °C occurring between 8.0 and 10.4 kbar at 750° C and between 9.5 and 11.3 kbar at 850° C. However, the writers' thermodynamic calculation of the divariant band indicates a more limited range of 0.65 and 0.7 kbar at 750° C and 850° C respectively, with an estimated error of ±0.2 kbar.  相似文献   

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