Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O

Beginning of melting and subsolidus relationships in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O have been experimentally investigated at pressures up to 20 kbars. The equilibria discussed involve the phases anorthite, sanidine, zoisite, muscovite, quartz, kyanite, gas, and melt and two invariant points: Point [Ky] with the phases An, Or, Zo, Ms, Qz, Vapor, and Melt; point [Or] with An, Zo, Ms, Ky, Qz, Vapor, and Melt.The invariant point [Ky] at 675° C and 8.7 kbars marks the lowest solidus temperature of the system investigated. At pressures above this point the hydrated phases zoisite and muscovite are liquidus phases and the solidus temperatures increase with increasing pressure. At 20 kbars beginning of melting occurs at 740 °C. The solidus temperatures of the quinary system K₂O-CaO-Al₂O₃-SiO₂-H₂O are almost 60° C (at 20 kbars) and 170° C (at 2kbars) below those of the limiting quaternary system CaO-Al₂O₃-SiO₂-H₂O.The maximum water pressure at which anorthite is stable is lowered from 14 to 8.7 kbars in the presence of sanidine. The stability limits of anorthite+ vapor and anorthite+sanidine+vapor at temperatures below 700° C are almost parallel and do not intersect. In the wide temperature — pressure range at pressures above the reaction An+Or+Vapor = Zo+Ms+Qz and temperatures below the melting curve of Zo+Ms+Ky+Qz+Vapor, the feldspar assemblage anorthite+sanidine is replaced by the hydrated phases zoisite and muscovite plus quartz. CaO-Al₂O₃-SiO₂-H₂O. Knowledge of the melting relationships involving the minerals zoisite and muscovite contributes to our understanding of the melting processes occuring in the deeper parts of the crust. Beginning of melting in granites and granodiorites depends on the composition of plagioclase. The solidus temperatures of all granites and granodiorites containing plagioclases of intermediate composition are higher than those of the Ca-free alkali feldspar granite system and below those of the Na-free system discussed in this paper.The investigated system also provides information about the width of the P-T field in which zoisite can be stable together with an Al₂SiO₅ polymorph plus quartz and in which zoisite plus muscovite and quartz can be formed at the expense of anorthite and potassium feldspar. Addition of sodium will shift the boundaries of these fields to higher pressures (at given temperatures), because the pressure stability of albite is almost 10kbars above that of anorthite. Assemblages with zoisite+muscovite or zoisite+kyanite are often considered to be products of secondary or retrograde reactions. The P-T range in which hydration of granitic compositions may occur in nature is of special interest. The present paper documents the highest temperatures at which this hydration can occur in the earth's crust.     

Two-feldspar geothermometry in granulite facies metamorphic rocks

A geothermometric technique based on equilibria between coexisting plagioclase and alkali feldspar was applied to quartzo-feldspathic granulites from Salvador, BA, Brazil. The conditions of metamorphism were determined to be in the range 750 ° C–800 ° C, 4–8 Kb, by comparison with experimental data on the stabilities of sapphirine, phlogopite and other minerals occurring in the associated rocks. Selected feldspar data gives temperatures near, but slightly below, this range. Several variants of the Wood and Banno model, as well as an empirical two-pyroxene geothermometer, were also tested and found to give temperatures which were apparently 50 °–100 ° high. The solubility of Al₂O₃ in orthopyroxene indicates temperatures which are about 200 ° to high, suggesting that Fe in the natural assemblages significantly changes relationships observed experimentally in MgO-Al₂O₃-SiO₂ systems.     

Stability of the assemblage orthopyroxene-sillimanite-quartz in the system MgO-FeO-Fe2O3-Al2O3-SiO2-H2O

The stability of coexisting orthopyroxene, sillimanite and quartz and the composition of orthopyroxene in this assemblage has been determined in the system MgO-FeO-Fe₂O₃-Al₂O₃-SiO₂-H₂O as a function of pressure, mainly at 1,000° C, and at oxygen fugacities defined mostly by the hematite-magnetite buffer. The upper stability of the assemblage is terminated at 17 kbars, 1,000° C, by the reaction opx+Al-silicate gar+qz, proceeding toward lower pressures with increasing Fe/(Fe+Mg) ratio in the system. The lower stability is controlled by the reaction opx+sill+qz cord, which occurs at 11 kbars in the iron-free system but is lowered to 9 kbars with increasing Fe/(Fe+Mg). Spinel solid solutions are stabilized, besides quartz, up to 14 kbars in favour of garnet in the iron-rich part of the system (Fe/(Fe+Mg)0.30). Ferric-ferrous ratios in orthopyroxene are increasing with increasing ferro-magnesian ratio. At least part of the generally observed increase in Al content with Fe²⁺ in orthopyroxene is not due to an increased solubility of the MgAlAlSiO₆ component but rather of a MgFe³⁺AlSiO₆ component. The data permit an estimate of oxygen fugacity from the composition of orthopyroxene in coexistence with sillimanite and quartz.     

Resetting of oxybarometers and oxygen isotope ratios in granulite facies orthogneisses during cooling and shearing,Adirondack Mountains,New York

The petrography, petrology, and oxygenisotope geochemistry of granulite-facies granitic and syenitic orthogneisses of the Diana and Stark complexes, Adirondack Mountains, New York, show that the extent and nature of resetting of isotopic and mineralogic systems is highly variable. There is a strong correlation between retrogression and shearing, and the rocks may be divided texturally into: (1) unsheared lithologies that preserve little-retrogressed pyroxene-or hornblendebearing peak-metamorphic mineralogies; and (2) sheared rocks that underwent retrogression, marked by the growth of late biotite, in centimetre-to metre-wide shear zones after the peak of metamorphism. Oxygen fugacities in the unsheared lithologies were estimated for reintegrated mineral compositions from magnetiteilmenite (Mt-Ilm) and ferrosilite-magnetic-quartz (Fs-Mt-Qtz) equilibria. Mt-Ilm yields logfO_2Mt-Ilm values of-15.9 to-17.6 (0.6 to 1.3 log units below the fayalite-magnetite-quartz buffer, FMQ) and temperatures of 670–745°C that agree with those from other geothermometry and phase equilibria studies. These data suggest that, aside from oxyexsolution of ilmenite from magnetite, the Fe-Ti system underwent only minor resetting during cooling, and the Fe-Ti oxides yield good estimates of peak-metamorphic temperatures and fO₂. In unsheared ilmenite + magnetite + orthopyroxene + quartz assemblages, values of logfO_2Mt-Ilm are lower than logfO_2Fs-Mt-Qtz by an average of 0.6 when the orthopyroxene activity model of Sack and Ghiorso is used. Minor resetting of the Fe-Ti oxides, analytical errors, and errors in the placement of end-member reactions probably account for this relatively small difference in fO₂ values. Whole-rock ¹⁸O values of unsheared Diana and Stark lithologies range from 4.0 to 10.3 reflecting pre-regional metamorphic oxygen-isotope ratios. Peak-metamorphic minerals preserve high-temperature oxygen-isotope fractionations, and, in many samples, the effective diffusion of oxygen in minerals ceased at higher temperatures than predicted from wet experimental diffusion data. These data suggest that the rocks did not contain an aqueous fluid phase during cooling. The combination of petrologic, isotopic, and textural data also permits a detailed study of shearing and retrogression. Ilmenites in the sheared lithologies underwent greater degrees of hematite loss than in the unsheared rocks, resulting in logfO_2Mt-Ilm values as low as-24.1 (3.1 log units below FMQ) and Mt-Ilm temperatures that are up to 175°C below regional estimates. Sheared rocks also have higher ¹⁸O values (up to 13.3). During shearing, ¹⁸O values of biotite, K-feldspar, and magnetite reset readily, while the degree of isotopic resetting of quartz correlates with the intensity for recrystallization.This paper is a contribution to IGCP Project 304, Lower Crustal Processes     

A granulite facies kalsilite-leucite-hibonite association from Punalur,Southern India

Summary Kalsilite, leucite and hibonite occur together with spinel, corundum, sphene, perovskite, Ti-phlogopite and K-feldspar in a granulite facies gneiss in the Punalur district in Kerala, southern India. Kalsilite-leucite-perovskite-phlogopite and kalsilite-hibonite-spinelcorundum formed distinct, texturally equilibrated assemblages during the granulite facies metamorphism. Sphene occurs as coronas on perovskite suggesting the retrograde breakdown of the perovskite-leucite association; leucite is partially altered to symplectites of K-feldspar and kalsilite, while hibonite shows partial replacement by corundum and perovskite in spinel-rich domains. Unlike other terrestrial hibonites the majority of the Punalur hibonites contain no significant rare earths (REE < 0.01 atoms per 190), with a composition approximated by Ca_0.85Ti_0.9Mg_0.25Fe_0.25Ali_10.4O₁₉ although a few zoned hibonites have REE rich cores with REE > 0.6 atoms per 19 O. Garnet-hypersthene granulites from Punalur and garnet-charnockites from elsewhere in Kerala suggest metamorphism at 700–800°C and 3.5–6.5 kbars; consistent with experimentally determined stability limit of leucite of low a(H₂O). The metamorphic conditions recorded by the Punalur assemblages testify to relatively low pressure conditions for a granulite facies terrain but are by no means unique. The scarcity of potassium feldspathoid in the metamorphic record must therefore be attributed to the exceptional compositional requirements of extreme silica undersaturation combined with low Na/K ratios.

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Eine Kalsilit-Leucite-Hibonit Paragenese in Granulit Fazies von Punalur, Süd-Indien

Zusammenfassung Kalsilit, Leuzit, and Hibonit kommen zusammen mit Spinell, Korund, Titanit, Perovskit, Ti-Phlogopit and K-Feldspat in einem granulitfaziellen Gneiss des Punalur-Distriktes in Kerala, Süd-Indien vor. Kalsilit-Leuzit-Perovskit-Phologopit and Kalsilit-Hibonit-Spinell-Korund bildeten wdhrend der Granulit-Fazies-Metamorphose deutliche Paragenesen, die texturell im Gleichgewicht sind. Titanit kommt als Koronas aufPerovskit vor und dies weist auf den retrograden Zerfall der Perovskit-Leuzit Paragenese hin. Leuzit ist teilweise zu Symplektiten von K-Feldspat und Kalsilit umgewandelt, während Hibonit Verdrängung durch Korund und Perovskit in spinellreichen Domänen zeigt. Im Gegensatz zu anderen terrestrischen Hiboniten, führt die Mehrzahl der Hibonite von Punalur, mit einer ungefähren Zusammensetzung von Ca_0.85Ti_0.9Mg_0.58Fe_0.25Ali_10.4O₁₉, keine wesentlichen Seltenen-Erd-Gehalte (SEE < 0.01 Atome per 19 0). Trotzdem gibt es einige wenige zonierte Hibonite, deren Kerne reich an SEE sind mit ESEE > 0.6 Atome per 19 O. Granat-Hypersthen Granulite aus Punalur and Granat-Charnockite von anderen Teilen Kerala's weisen auf eine Metamorphose bei 700–800°C und 3.5–6.5 kbar hin; dies ist in guter Übereinstimmung mit der experimentell bestimmten Stabilitätsgrenze von Leuzit bei niederigen a(H₂O). Die metamorphen Bedingungen, die die Punalur-Paragenesen dokumentieren, zeigen relativ niedrige Druckbedingungen für ein Granulit-Fazies Terrain an; das ist aber keineswegs einmalig. Die Seltenheit von Kali-Feldspathoiden während der metamorphen Entwicklung muß deshalb auf die ungewöhnlichen Erfordernisse extremer Silizium-Untersättigung, zusammen mit niedrigen Na/K-Verhältnissen, zurückgehen.

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With 6 figures     

Melting and subsolidus reactions in the system K2O-CaO-Al2O3-SiO2-H2O: corrections and additional experimental data

Melting relationships in the system K₂O-CaO-Al₂O₃-SiO₂-H₂O have been reinvestigated using Schreinemakers analysis and hydrothermal experiments. The reaction sanidine+muscovite+zoisite+quartz+vapor =melt has been bracketed at 10, 15, and 20 kbars and 670–680, 680–690, and 690–700° C, respectively and it marks the lowest solidus temperatures in the system investigated.Below 10 kbars, experimental data on the beginning of melting in zoisite- or muscovite-bearing anorthite+sanidine assemblages have been obtained, which are not showing any differences and therefore point to melt compositions close to the feldspar-quartz join.     

Stability of the assemblage cordierite +K feldspar+quartz

Under hydrous conditions the stability field of the assemblage Mg-cordierite+K feldspar+quartz is limited on its low-temperature side by the breakdown of cordierite+K feldspar into muscovite, phlogopite and quartz, whereas the high-temperature limit is given by eutectic melting. The compatibility field of the assemblage ranges from 530° C to 745° C at 1 kbar , from 635 to 725° C at 3 kbars , from 695 to 725° C at 5 kbars and terminates at 5.5 kbars . Most components not considered in the model system will tend to restrict this field even more. However, the condition < P _total will increase the range of stable coexistence drastically, making the assemblage common at elevated temperatures from contact metamorphic rocks up to intermediate pressure granulites of appropriate bulk composition.     

Carbon isotopic fractionation between CO2 vapour,silicate and carbonate melts: an experimental study to 30 kbar

The carbon isotopic fractionation between CO₂ vapour and sodamelilite (NaCaAlSi₂O₇) melt over a range of pressures and temperatures has been investigated using solid-media piston-cylinder high pressure apparatus. Ag₂C₂O₄ was the source of CO₂ and experimental oxygen fugacity was buffered at hematite-magnetite by the double capsule technique. The abundance and isotopic composition of carbon dissolved in sodamelilite (SM) glass were determined by stepped heating and the ¹³C of coexisting vapour was determined directly by capsule piercing. CO₂ solubility in SM displays a complex behavior with temperature. At pressures up to 10 kbars CO₂ dissolves in SM to form carbonate ion complexes and the solubility data suggest slight negative temperature dependence. Above 20 kbars CO₂ reacts with SM to form immiscible Na-rich silicate and Ca-rich carbonate melts and CO₂ solubility in Na-enriched silicate melt rises with increasing temperature above the liquidus. Measured values for carbon isotopic fractionation between CO₂ vapour and carbonate ions dissoived in sodamelilite melt at 1200°–1400° C and 5–30 kbars average 2.4±0.2, favouring¹³C enrichment in CO₂ vapour. The results are maxima and are independent of pressure and temperature. Similar values of 2 are obtained for the carbon isotopic fractionation between CO₂ vapour and carbonate melts at 1300°–1400° C and 20–30 kbars.     

Melting and subsolidus reactions in the system K2O−CaO−MgO−Al2O3−SiO2−H2O: experiments and petrologic application

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 muscovite_ss +zoisite+quartz+vapor=liquid+kyanite+phlogopite_ss 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 tremolite_ss was reversibly observed from the assemblage phlogopite_ss+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 muscovite_ss+talc_ss+ tremolite_ss=phlogopite_ss+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 phlogopite_ss+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.     

The influence of the fluid phase composition on the solidus temperatures in the haplogranite system NaAlSi3O8-KAlSi3O8-SiO2-H2O-CO2

The solidus temperatures in the haplogranite-system NaAlSi₃O₈-KAlSi₃O₈-SiO₂-H₂O-CO₂ have been determined up to 15 kbar for a constant molar ratio of sodium to potassium of 11 and for fluid compositions ranging from pure water to pure carbon dioxide. The data for the water-saturated solidus are virtually identical with those of previous studies. At constant pressure, the solidus curve as a function of the fluid phase composition exhibits a point of inflection in the range of the water-rich compositions. This phenomenon is attributed to chemical interactions between the CO₂ and the H₂O in the silicate melt. The point of inflection disappears if the CO₂ in the gas phase is replaced by molecular nitrogen. The CO₂-saturated solidi have been measured at 2 and 5 kbars. The data at 5 kbar indicate a melting point depression in the order of 40° C compared to the dry solidus of Huang and Wyllie (1975). The experimental data can be used to estimate the melting temperatures of common quartz and feldspar bearing crustal rocks under the conditions of granulite facies metamorphism. Since for most fluid phase compositions, the solidus curves are very steep in the P, T-diagram, the beginning of melting is nearly exclusively determined by the fluid composition and almost independent of pressure between about 2 and more than 10 kbar. Therefore, the onset of partial melting in quartz and feldspar containing rocks under granulite facies conditions can be used to estimate the composition of a coexisting H₂O-CO₂ fluid phase if geothermometric data are available. The temperature range between the beginning of granulite facies metamorphism and the initiation of melting expands with increasing carbon dioxide content in the H₂O-CO₂ fluid phase. At a CO₂ molar fraction of 0.9, this range extends from about 600° C to 900° C and is almost independent of pressure.     

Preliminary phase relations involving glaucophane and applications to high pressure petrology: new heat capacity and thermodynamic data

New heat capacity measurements and cell volume data are presented for a very magnesian glaucophane from a Tauern Window eclogite. These data are combined with estimated entropy, thermal expansion, and compressibility data to generate an enthalpy of formation for glaucophane from experimentally determined phase equilibria. The data are supported by preliminary experiments of the author and provide consistent calculations on the pressure of formation of the Tauern eclogites and on the position of the blueschist-greenschist transformation reaction as studied experimentally by Maruyama et al. (1986). The resulting thermodynamic data for glaucophane may be combined with the dataset of Holland and Powell (1985) to calculate phase relations for blueschists and eclogites. The stability of magnesian glaucophane lies in the pressure range between 8 and 32 kbars at 400° C and between 13 and 33 kbars at 600° C, and the unusual eclogite assemblage of glaucophane+kyanite from the Tauern Window is restricted to pressures above 20 kbars at high water activity.     

Formation of sapphirine during retrogression of a basic high-pressure granulite,Roan, Western Gneiss Region,Norway

Sapphirine-bearing rocks occur in the northern part of the Western Gneiss Region, Vestranden, central Norway. The sapphirine-bearing rocks are characterized by a high MgO/(MgO + FeO) ratio, high Al₂O₃, MgO and CaO, and low SiO₂ contents. These rocks form layers within larger complexes which originated as layered magmatic rocks. High PT-metamorphism produced a cpx+ky+gt assemblage. The P and T estimates are P = 14.5±2 kbar and T= 870±50° C. During retrogression, the high-P granulite assemblage broke down to form an intermediate-P granulite mineralogy comprising orthopyroxene, spinel, anorthite, andesine, sapphirine and corundum. Textural relationships suggest that sapphirine formed by the reaction: spinel+kyanite sapphirine+corundum, and probably also by a reaction between corundum, spinel and orthopyroxene. All reactions took place within the stability field of kyanite. Textural and micro-chemical relationships indicate equilibrium, conditions during the peak metamorphism, whereas pronounced disequilibrium characterizes the mineral associations formed during the early retrogression at low P _H2O. The investigation shows that parts of the northern segment of the Western Gneiss Region underwent a metamorphic evolution similar to the Caledonian one recorded from eclogite/granulite terrains further south.     

Comparative petrology of Archaean anorthosites in amphibolite and granulite facies terranes, SW Greenland

We report new field and petrographic observations, and mineral-chemical data, on the amphibolite-facies Buksefjorden and granulite-facies Nordland anorthosites, which occur in different tectonostratigraphic terranes within the Archaean gneiss complex of SW Greenland. The Buksefjorden body [from the Akulleq (middle) terrane] is dominated by plagioclase and Ca-amphibole, but shows widespread effects of retrograde hydration (epidote, chlorite). Most plagioclase compositions are in the An_60–82 range, with the majority of samples showing average core compositions ∼An₇₆, whereas rims or recrystallized margins are ∼An₆₅. Most grains in the An_70–82 range display optically visible Huttenlocher intergrowths. Amphiboles at Buksefjorden are mainly magnesio-hornblende with X _Mg ranging from 0.70 to 0.45. The Nordland anorthosite [from the Akia (northern) terrane] is also dominated by plagioclase and Ca-amphibole, but contains additional clinopyroxene (∼Ca₄₇Mg₃₈Fe₁₅) as well as minor orthopyroxene (∼En₆₈), spinel and corundum. Plagioclase at Nordland shows an equilibrated, equigranular texture, consistent with prolonged slow cooling from high temperatures. Despite this textural equilibration, plagioclase at Nordland shows a striking range of compositions from An₂₈ to An₉₇, most of which is found in single thin sections. A distinctive feature is the presence of discrete anorthite (+ spinel ± corundum) domains in some samples. Although a number of explanations may apply, we consider these domains to result from prograde mass transfer reactions involving Ca-amphibole and plagioclase. Amphibole compositions at Nordland show similar X _Mg to those at Buksefjorden, but are more aluminous, alkalic, and titanian. This shift to more pargasitic compositions is consistent with the contrasts in metamorphic grade between the two anorthosite bodies. At Buksefjorden, there is no correlation between the amount of modal Ca-amphibole and plagioclase composition, which would be expected if amphibole was produced solely through metamorphism. Our results suggest, alternatively, that the primary igneous mineralogy of these rocks may have been plagioclase (∼An₇₆) + hornblende + pyroxene + magnetite. The primary mineralogy at Nordland is less certain, but it is noteworthy that no rocks contain anorthite of unambiguous igneous origin, in contrast to some other occurrences of Archaean anorthosites. Received: 17 January 1996 / Accepted: 12 March 1997     

Metasomatism of a depleted granulite facies terrain in the Arunta Block,central Australia

Geochemical investigations in the Utralanama Block, an intermediate pressure granulite facies terrain in the Arunta Block, central Australia, has revealed several anomalous features, not consistent with the depletion of granitophile components generally considered to accompany granulite facies metamorphism. However, other geochemical features are indicative of depletion. The mean K₂O for the Utralanama Block is exceptionally low relative to most other granulite facies terrains, but Rb contents are comparatively high. Consequently, the mean K/Rb ratio is relatively low for granulite facies terrains as is the mean Ba/Rb ratio, whilst mean K/Sr and Rb/Sr ratios are much higher than usual for such terrains. Only the K/Ba ratio shows equivalent values to depleted terrains elsewhere.Comparison of these ratios for the three main compositional groups of rocks in the Utralanama Block reveals that for mafic rocks all the above ratios are characteristic of extreme depletion, whereas, for all but the K/Ba ratio, mean ratios for the pelitic rocks, and to a lesser extent for the quartzofeldspathic rocks approach normal crustal values or values for metasomatic rocks. The abnormally high Rb/Sr ratios of these rocks compared to average crustal rocks suggest, however, that metasomatism is the cause of the anomalous geochemical features of the Utralanama Block, and this is supported by field and microstructural evidence. Thus, Rb/Sr ratios appear to be useful indicators of metasomatism where no gross mineralogical or microstructural evidence for metasomatism is obvious, and under such conditions the K/Ba ratio may be more reliable than the K/Rb ratio for indicating prior depletion of the terrain.     

Calculated mineral equilibria in the greenschist-blueschist-eclogite facies in Na2O−FeO−MgO−Al2O3−SiO2−H2O

The new, greatly expanded internally-consistent dataset of Holland and Powell includes thermodynamic data for a wide range of mineral end-members in common rock-forming minerals, in particular, including FeMg_-1 substitutions in glaucophane, garnet, chloritoid and carpholite, and FeMg_-1 and MgSiAl_-1Al_-1 substitutions in talc and chlorite. Moreover, we have the uncertainties and correlations for these data. With the data, we have calculated the full pressure-temperature phase diagram for the system Na₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O (NFMASH) for quartz (or coesite) and H₂O in excess, in the range 300°–800°C and 5–50 kbars. By solving the set of non-linear equations formed by the equilibrium relationships for an independent set of equations between the end-members in an assemblage in NFMASH, the compositions of the minerals (and PT) can be calculated. Thus the changes in MgSiAl_-1Al_-1 along NMASH reactions, and FeSiAl_-1Al_-1 along NFASH reactions, are calculated, and the changes in FeMg_-1 and MgSiAl_-1Al_-1 along NFMASH reactions are calculated. From this information it is straightforward to generate PT diagrams for specific rock compositions. Mineral assemblages and mineral compositional changes in the phase diagram are discussed in relation to greenschist, blueschist and eclogite facies assemblages in metapelitic rocks. It is found that the correspondence between the predictions of the phase diagrams and the observations on rocks is remarkably good. When semiquantitative extensions of the phase diagram to include Ca(MgFe)_-1, NaSiCa_-1Al_-1, Fe³⁺Al_-1 and KNa_-1 substitutions are taken into account the agreement is essentially complete.     

Sapphirine and spinel phase relationships in the system FeO-MgO-Al2O3-SiO2-TiO2-O2 in the presence of quartz and hypersthene

Sapphirine and spinel can accommodate significant ferric iron and therefore the mineral equilibria involving these phases must be sensitive to a(O₂). In this paper we examine the theoretical phase relationships involving sapphirine and spinel in addition to sillimanite, garnet, cordierite, rutile, hematite-ilmenite solid solution (henceforth ilmenite), and magnetite-ulvospinel solid solution (henceforth magnetite), in the presence of quartz and hypersthene in the system FeO-MgO-Al₂O₃-SiO₂-TiO₂-O₂ (FMASTO), with particular reference to the topological inversion in P-T postulated by Hensen (Hensen 1986). Documented natural associations suggest that the appropriate topology for assemblages involving magnetite and ilmenite is Hensen's higher a(O₂) one, while, in contrast, the topology for assemblages involving ilmenite and rutile is the lower a(O₂) one. The exact configuration of the inversion between these two topologies remains uncertain because of uncertainties in the ferric/ferrous iron partitioning between sapphirine and spinel-cordierite at high temperatures. By comparison with experimental data and natural occurences, the sillimanite-sapphirine-cordierite-garnet-hypersthene-quartz assemblage is in equilibrium at about 1000°–1020° C and 7–8 kbars, while sapphirine-cordierite-spinel-garnet-hypersthene-quartz occurs at temperatures in excess of those attainable during crustal metamorphism, for ilmenite-rutile buffered assemblages. This implies that sapphirine-rutil-ehypersthene-quartz assemblages, as found in the Napier Complex, Antarctica, can only occur at > 1000° C. Also, spinel-rutile-hypersthene-quartz assemblages should not be found in rocks because temperatures in excess of 1100° C are expected to be involved in their formation. The temperatures of formation of spinel-sillimanite-sapphirine-garnethypersthene-quartz, sapphirine-spinel-cordierite-sillimanite-hypersthene-quartz, and sillimanite-spinel-cordieritegarnet-hypersthene-quartz in assemblages buffered by magnetite and ilmenite are less well constrained, but are likely to be in the range 900°–1000° C. These conclusions apply to rocks with compositions close to FMASTO; the perturbing effects of substantial concentrations of additional components, in particular Ca, mainly in garnet, and Zn and Cr, mainly in spinel, may invalidate these conclusions.     

Fe-rich cordierites from acid volcanic rocks,an optical and x-ray single-crystal structure study

Low-cordierites from volcanic rocks of Tuscany (Italy), Lipari (Italy), and of the Cerberean Cauldron (Australia) were investigated. Both single crystal structure refinements and optical data indicate that the Italian samples contain only low concentrations of volatiles (<0.3 wt.%), whereas in the crystals from the Cerberean Cauldron more than 50% of the structural channels are occupied, preferentially by H₂O (1.6–1.9 wt.%). This high volatile concentration is in qualitative agreement with the estimated p,T-conditions (4–4.5 kbar at 750–780° C) of the magma prior to eruption. In contrast, the Italian cordierites have formed at temperatures above 950° C and pressures below 2 kbars. Low-cordierites of volcanic origin reveal the same high degree of Si, Al-ordering as observed for low-cordierites from metamorphic rocks and pegmatites. The crystals studied possess F(mol)=(Fe+Mn)/(Fe+Mn+Mg)>0.4 and provide additional information about the crystal structure of Fe-rich cordierites. With increasing FeMg substitution the mean T₁1(Al)-O distance decreases slightly, which is probably not caused by substitution of smaller cations on t₁1 but by angular distortion of the tetrahedron.     

Melting relations of muscovite-granite to 35 kbar as a model for fusion of metamorphosed subducted oceanic sediments

Muscovite-granite was reacted in cold-seal pressure vessels at 2 kbar and in pistoncylinder apparatus between 10 and 35 kbar, with just 0.6 weight per cent water structurally bound in 14 modal per cent muscovite, and with additional water contents varying to 50 weight per cent. Phase relationships are presented through the melting interval with excess water, and with no free water added. Selected reactions above 10 kbars have been successfully reversed. An isobar at 15 kbar shows the effect of varying water contents on the mineral phase boundaries for vapor-present and vapor-absent conditions. For the dry rock, temperatures for the solidus and liquidas (quartz-out) curves, respectively, are 10 kbar-760° C, 1160° C; 15 kbar-810° C, 1220° C; 25 kbar-880° C; 1340° C; 35 kbar-1040° C, 1460° C. The solidus curve corresponds to the melting of muscovite + quartz. With water vapor present, the solidus is considerably lower, 15 kbar-610° C, 25 kbar-665° C. Water solubility in the liquid at 15 kbar is 24±3 weight per cent. Maximum temperatures for quartz and feldspars in the vapor-absent region decrease considerably with increasing water content. Temperatures for the quartz-out curve at 15 kbars are 0.6 % H₂O-1230° C; 24 % H₂O-760° C. At 15 kbars for low water contents, water-undersaturated liquid coexists with quartz and feldspars through hundreds of degrees. Subducted pelagic sediments which metamorphosed to muscovitebearing quartzo-feldspathic rocks would undergo two episodes of melting, beginning at different depths: (1) the first liquid dissolves all pore fluid, and transports it away when it escapes from the crystalline host, (2) reaction of muscovite yields a second liquid, with less dissolved water. According to two published thermal models for a lithosphere slab dipping at 45°, the depths would be (a) 60 km and 92 km, or (b) 17 km and 21 km. Magmas generated by partial fusion in subducted oceanic crust are cooler than the overlying crustal layers and the mantle above the slab by as much as 200° C to 300° C. This must lead to intrusion of relatively cool magma into hot rock. Consequent heating of the magma increases its prospects of reaching high levels in the upper mantle or crust before it solidifies by crossing the solidus curve.     

Pyroxene geothermometry of some granulite facies rocks

Wood-and-Banno temperatures for the coexisting pyroxenes of equilibrated metamorphic rocks in the hornblende granulite subfaoies fall in the range 780–860° C. Minimum temperature estimates for granulites include 760–790 °C, from the dehydration of hornblende to an orthopyroxene assemblage, and about 800 °C, from other evidence. The pyroxene temperatures are generally consistent with these temperature estimates, and are certainly not too low or more than 50 ° too high. Pyroxene temperatures for the three subzones of Broken Hill granulites increase away from the orthopyroxene isograd and are sufficiently precise that the difference between the lowest and intermediate gubzones is statistically significant. Temperatures for pyroxenes in pyroxene-granulite subfacies rocks are greater than 860 °C. The internal consistency, precision and apparent accuracy of the Wood-and-Banno pyroxene geothermometer in the metamorphic temperature range make it an important tool.     

The restricted stability of osumilite under hydrous conditions in the system K2O-MgO–Al2O3–SiO2–H2O

Osumilite_ss was synthesized as a single phase product in the model system K₂O-MgO-Al₂O₃-SiO₂ at 800° C/ 0.5 Kbar water pressure and at 800° to 840° C/1.0 Kbar total pressure with 0.3 in the gas phase. The experimentally determined solid solubility range of synthetic osumilites can be expressed by the formula KMg₂(Al_3-xMg_x) (Al_2–xSi_10+x)O₃₀ with 0x0.4. A survey of sixteen chemical analyses of natural osumilites from eleven occurrences shows a solid solubility characterized by 0x0.6. Reversed stability experiments for the synthetic osumilite KMg₂(Al_2.75Mg_0.25)(Al_1.75Si_10.25)O₃₀ determined at water pressure equal to total pressure demonstrate its restriction to water pressures below 0.8 Kbar (at 0.5 Kbar, the stability range is between 765° and 800° C). At the lower thermal stability limit osumilite+H₂O vapor break down to cordierite+K feldspar+phlogopite_ss+quartz, at the higher one to cordierite+K feldspar+phlogopite+liquid. Reduction of water fugacity will expand the stability field largely by shifting the lower and higher thermal stability limits to lower and higher temperatures, respectively. The dependence of osumilite stability on water fugacity makes osumilite a sensitive indicator mineral for dry conditions in rocks formed at total pressures higher than about 0.8 Kbar.