Beginning of melting and composition of first melts in the system Qz-Ab-Or-H2O-CO2

Solidus temperatures have been determined for minimum melt compositions in the system Qz(SiO₂)-Ab(NaAlSi₃O₈)-Or(KAlSi₃O₈) at P(fluid)=2,5 and 10 kbar and at various water activities. The dry solidus was investigated in a dry argon environment. Water activities (aH₂O) between 0.0 and 1.0 were obtained by using H₂O-CO₂ mixtures. The Or/Ab+Or ratio of first melts increases considerably with decreasing water activity. At 10 kbar it is 0.28 in the water-saturated system and 0.56 at water activity 0.1. The Qz-content does not change with changing water activities. The Ab-content of minimum melts formed at high pressures and low aH₂O may remain almost constant in ascending magmas that are cooling and crystallizing. Qz-content increases at the expense of the Or-component. Solidus temperatures decrease considerably when aH₂O increases slightly from zero. At 10 kbar, the temperature difference between dry melting and the solidus for aH₂O=0.1 is 120°C. The influence of pure CO₂ on the solidus is very limited in the investigated P-T range. The solidus is approximatively 760°C at aH₂O=0.5 between 2 and 10 kbar and approximatively 830°C at aH₂O=0.3. This means that melting of quartz-feldspar assemblages may induce dehydration reactions at P-T conditions of the granulite facies.     

Carbon in silicate liquids: the systems NaAlSi3O8-CO2, CaAl2Si2O8-CO2, and KAlSi3O8-CO2

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     

P-T-X effects on equilibrium carbonate-H2O-CO2-NaCl dihedral angles: constraints on carbonate permeability and the role of deformation during fluid infiltration

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.     

Fluid evolution during metamorphism at increasing pressure: carbonic- and nitrogen-bearing fluid inclusions in granulites from Øksfjord,north Norwegian Caledonides

Three successive metamorphic stages M1, M2 and M3 have been distinguished in polymetamorphic granulite facies quartz-feldspathic gneisses from the Seiland Igneous Province, Caledonides of northern Norway. An early period of contact metamorphism (M1; 750–950°C, ca. 5 kbar) was followed by cooling, accompanied by strong shearing and recrystallization at intermediate-P granulite facies conditions (M2; 700–750°C, 5–6kbar). High-P granulite facies (M3; ca. 700°C, 7–8 kbar) is related to recrystallization in narrow ductile shear zones and secondary growth on M2 minerals. On the basis of composition, fluid inclusions in cordierite, quartz and garnet can be divided into three major types: (1) CO₂ inclusions; (2) mixed CO₂–N₂ inclusions; (3) N₂ inclusions. Fluid chronology and mineral assemblages suggest that the earliest inclusions consist of pure CO₂ and were trapped at the M1 contact metamorphic episode. A carbonic fluid was also present during the intermediate-P granulite facies M2 metamorphism. The CO₂-rich inclusions in M2 garnet can be divided into two generations, an early lower-density and a late higher-density, with isochores crosscutting the P-T box of M2 and M3, respectively. The nitrogen-rich fluids were introduced at a late stage in the fluid evolution during the high-P M3 event. The mixed CO₂–N₂ inclusions, with density characteristics compatible with M3 conditions, are probably produced from intersection between pre-existing pure CO₂ inclusions and N₂ fluids introduced during M3. The fluid inclusion data agree with the P-T evolution established from mineral assemblages and mineral chemistry.     

Polymetamorphism in the mainland Lewisian complex,NW Scotland – phase equilibria and geochronological constraints from the Cnoc an t’Sidhean suite

The metamorphic evolution of rocks cropping out near Stoer, within the Assynt terrane of the central region of the mainland Lewisian complex of NW Scotland, is investigated using phase equilibria modelling in the NCKFMASHTO and MnNCKFMASHTO model systems. The focus is on the Cnoc an t’Sidhean suite, garnet‐bearing biotite‐rich rocks (brown gneiss) with rare layers of white mica gneiss, which have been interpreted as sedimentary in origin. The results show that these rocks are polymetamorphic and experienced granulite facies peak metamorphism (Badcallian) followed by retrograde fluid‐driven metamorphism (Inverian) under amphibolite facies conditions. The brown gneisses are inferred to have contained an essentially anhydrous granulite facies peak metamorphic assemblage of garnet, quartz, plagioclase and ilmenite (±rutile, K‐feldspar and pyroxene) with biotite, hornblende, muscovite, chlorite and/or epidote as hydrous retrograde minerals. P–T constraints imposed by phase equilibria modelling imply conditions of 13–16 kbar at >900 °C for the Badcallian granulite facies metamorphic peak, consistent with the field evidence for partial melting in most lithologies. The white mica gneiss comprises a muscovite‐dominated matrix containing porphyroblasts of staurolite, corundum, kyanite and rare garnet. Previous studies have suggested that staurolite, corundum, kyanite and muscovite all grew at the granulite facies peak, with partial melting and melt loss producing a highly aluminous residue. However, at the inferred peak P–T conditions, staurolite and muscovite are not predicted to be stable, suggesting they are retrograde phases that grew during amphibolite facies retrograde metamorphism. The large proportion of mica suggests extensive H₂O‐rich fluid‐influx, consistent with the retrograde growth of hornblende, biotite, epidote and chlorite in the brown gneisses. P–T conditions of 5.0–6.5 kbar at 520–550 °C are derived for the Inverian event. In situ dating of zircon from samples of the white mica gneiss yield apparent ages that are difficult to interpret. However, the data are permissive of granulite facies (Badcallian) metamorphism having occurred at c. 2.7–2.8 Ga with subsequent fluid driven (Inverian) retrogression at c. 2.5–2.6 Ga, consistent with previous interpretations.     

Partial melting of metagreywacke: a calculated mineral equilibria study

Greywacke occurs in most regionally metamorphosed orogenic terranes, with depositional ages from Archean to recent. It is commonly the dominant siliciclastic rock type, many times more abundant than pelite. Using calculated pseudosections in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O system, the partial melting of metagreywacke is investigated using several natural protolith compositions that reflect the main observed compositional variations. At conditions appropriate for regional metamorphism at mid‐crustal depths (6–8 kbar), high‐T subsolidus assemblages are dominated by quartz, plagioclase and biotite with minor garnet, orthoamphibole, sillimanite, muscovite and/or K‐feldspar (±Fe–Ti oxides). Modelled solidus temperatures are dependent on bulk composition and vary from 640 to 690 °C. Assuming minimal melting at the H₂O‐saturated solidus, initial prograde anatexis at temperatures up to ～800 °C is characterized by very low melt productivity. Significant melt production in commonly occurring (intermediate) metagreywacke compositions is controlled by the breakdown of biotite and production of orthopyroxene (±K‐feldspar) across multivariant fields until biotite is exhausted at 850–900 °C. Assuming some melt is retained in the source, then at temperatures beyond that of biotite stability, melt production occurs via the consumption of plagioclase, quartz and any remaining K‐feldspar as the melt becomes progressively more Ca‐rich and H₂O‐undersaturated. Melt productivity with increasing temperature across the melting interval in metagreywacke is generally gradational when compared to metapelite, which is characterized by more step‐like melt production. Comparison of the calculated phase relations with experimental data shows good consistency once the latter are considered in terms of the variance of the equilibria involved. Calculations on the presumed protolith compositions of residual granulite facies metagreywacke from the Archean Ashuanipi subprovince (Quebec) show good agreement with observed phase relations. The degree of melt production and subsequent melt loss is consistent with the previously inferred petrogenesis based on geochemical mass balance. The results show that, for temperatures above 850 °C, metagreywacke is sufficiently fertile to produce large volumes of melt, the separation from source and ascent of which may result in large‐scale crustal differentiation if metagreywacke is abundant.     

The influence of H2O-H2 fluids and redox conditions on melting temperatures in the haplogranite system

Solidus temperatures of quartz–alkali feldspar assemblages in the haplogranite system (Qz-Ab-Or) and subsystems in the presence of H₂O-H₂ fluids have been determined at 1, 2, 5 and 8 kbar vapour pressure to constrain the effects of redox conditions on phase relations in quartzofeldspathic assemblages. The hydrogen fugacity (f _H2) in the fluid phase has been controlled using the Shaw membrane technique for moderately reducing conditions (f _H2 < 60 bars) at 1 and 2 kbar total pressure. Solid oxygen buffer assemblages in double capsule experiments have been used to obtain more reducing conditions at 1 and 2 kbar and for all investigations at 5 and 8 kbar. The systems Qz-Or-H₂O-H₂ and Qz-Ab-H₂O-H₂ have only been investigated at moderately reducing conditions (1 and 5 kbar) and the system Qz-Ab-Or-H₂O-H₂ has been investigated at redox conditions down to IW (1 to 8 kbar). The results obtained for the water saturated solidi are in good agreement with those of previous studies. At a given pressure, the solidus temperature is found to be constant (within the experimental precision of ± 5°C) in the f _H2 range of 0–75 bars. At higher f _H2, generated by the oxygen buffers FeO-Fe₃O₄ (WM) and Fe-FeO (IW), the solidus temperatures increase with increasing H₂ content in the vapour phase. The solidus curves obtained at 2 and 5 kbar have similar shapes to those determined for the same quartz - alkali feldspar assemblages with H₂O-CO₂- or H₂O-N₂-bearing systems. This suggests that H₂ has the behaviour of an inert diluent of the fluid phase and that H₂ solubility in aluminosilicate melts is very low. The application of the results to geological relevant conditions [HM (hematite-magnetite) > f _O2 > WM] shows that increasing f _H2 produces a slight increase of the solidus temperatures (up to 30 °C) of quartz–alkali feldspar assemblages in the presence of H₂O-H₂ fluids between 1 and 5 kbar total pressure. Received: 4 March 1996 / Accepted: 22 August 1996     

Stability of phlogopite-quartz and sanidine-quartz: A model for melting in the lower crust

The melting of phlogopite-quartz and sanidine-quartz under vapor-absent conditions and in the presence of H₂O-CO₂ vapor have been determined from 5–20 kbar. In the lower crust (P=6–10 kbar), phlogopite + quartz melts incongruently to enstatite + liquid at temperatures as low as 710° C in the presence of H₂O. When the activity of water is sufficiently reduced by addition of CO₂, phlogopite + quartz undergoes a dehydration reaction to enstatite + sanidine + vapor, for example at 790±10° C, 5 kbar, with \(X_{H_2 O}^V\) =0.35. In the absence of vapor, phlogopite + quartz is stable up to a maximum temperature of 900° C in the crust; at higher temperatures this assemblage melts incongruently to enstatite + sanidine + liquid. The melting of sanidine-quartz in the presence of H₂O-CO₂ vapor shows marked topological differences from melting in the system albite-H₂O-CO₂, and as a result, apparent activity coefficients for water calculated from sanidine-quartz H₂O-CO₂ are less than those calculated from albite-H₂O-CO₂ by up to a factor of five. These data shed light on anatexis in the lower crust, but uncertainties related to ordering of Al and Si in natural and synthetic micas forestall a more rigorous analysis. Nevertheless, maximum temperatures for some granulite terranes can be established.     

Experimental phase relations of hydrous peridotites modelled in the system H2O-CaO-MgO-Al2O3,-SiO2

The hydration of peridotites modelled by the system H₂O-CaO-MgO-Al₂O₃-SiO₂ has been treated theoretically after the method of Schreinemakers, and has been investigated experimentally in the temperature range 700°–900° C and in the pressure range of 8–14 kbar. In the presence of excess forsterite and water, the garnet- to spinel-peridotite transition boundary intersects the chlorite dehydration boundary at an invariant point situated at 865±5° C and 15.2±0.3 kbar. At lower pressures, a model spinel lherzolite hydrates to both chlorite- and amphibole-bearing assemblages at an invariant point located at 825±10° C and 9.3±0.5 kbar. At even lower pressures the spinel-to plagioclase-peridotite transition boundary intersects the dehydration curve for amphibole+forsterite at an invariant point estimated to lie at 855±10° C and 6.5±0.5 kbar.Both chlorite and amphibole were characterized along their respective dehydration curves. Chlorite was found to shift continuously from clinochlore, with increasing temperature, to more aluminous compositions. Amphibole was found to be tremolitic with a maximmum of 6 wt.% Al₂O₃.The experimentally determined curves in this study were combined with the determined or estimated stability curves for hydrous melting, plagioclase, talc, anthophyllite, and antigorite to obtain a petrogenetic grid applicable to peridotites, modelled by the system H₂O-CaO-MgO-Al₂O₃-SiO₂, that covers a wide range of geological conditions. Direct applications of this grid, although quite limited, can be made for ultramafic assemblages that have been extensively re-equilibrated at greenschist to amphibolite facies metamorphism and for some highgrade ultramafic assemblages that display clear signs of retrogressive metamorphism.     

Melting of albite and dehydration of brucite in H2O–NaCl fluids to 9 kbars and 700–900°C: implications for partial melting and water activities during high pressure metamorphism

 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     

Metastable melting in the granite system Qz-Or-Ab-An-H2O

Time studies were performed in the quinary system Qz-Or-Ab-An-H₂O at kbars and T=665 ° and 660 ° C. Starting material was a mixture of quartz, alkali feldspar Or₈₀ and plagioclase An₃₁. The compositions of plagioclases of run products were determined and compared with the plagioclase of stable solidus conditions.The solidus of the granite system was fixed at P _HäO=5 kbars using various plagioclase — and appropriate alkali feldspar — compositions besides quartz in the starting mixture (Fig. 1).The results of time studies (Table 3 and Fig. 3) reveal metastable melting in the granite system Qz-Or-Ab-An-H₂O. Plagioclase melts almost stoichiometrically. The new plagioclase compositions formed during melting of cotectic compositions approach the theoretically expected stable plagioclase compositions only extremely slowly. An extrapolation of the data achieved in run times of 5–1,500 h indicates attainment of equilibrium after 10¹⁴ years. Metastable melting of granitic compositions is not only considered as an experimental problem but also as a rock forming process in nature.     

The effect of feldspar on quartz-H2O−CO2 dihedral angles at 4 kbar,with consequences for the behaviour of aqueous fluids in migmatites

An investigation was made of the effect of trace amounts of feldspar (Na and/or K) on dihedral angles in the quartz-H₂O-CO₂ system at 4 kbar and 450–1050°C. Quartz-quartz-H₂O dihedral angles in feldspar-bearing quartz aggregates are observed to be the same as those in pure quartz aggregates at temperatures below 500°C. Above this temperature, they decrease with increasing temperature until the solidus. The final angle at the inception of melting is about 65° for microcline-quartz-H₂O and microcline-albite-quartz-H₂O, and much less than 60° (the critical value for formation of grain-edge fluid channels in an isotropic system) for the albite-quartz-H₂O system. CO₂ was observed to produce a constant quartz-quartz-fluid dihedral angle of 97° in feldspar-bearing quartz aggregates at all temperatures studied. Also examined were the dihedral angles for the two co-existing supersolidus fluids in quartz aggregates. In all systems the quartz-volatile fluid angle is greater than 60°, whereas the quartz-melt angle is lower than 60°. Both super-solidus angles decrease with increasing temperature. The transition from nonconnected to connected poro- sity with increasing temperature observed in the quartz-albite-H₂O system some tens of degrees below the solidus (termed a permeability transition), if a common feature of rocks near their melting points, will play an important role in controlling the permeability of high-grade rocks to aqueous fluids. Received: 27 October 1993 / Accepted: 11 July 1994     

Fluids in granulites of the Southern Marginal Zone of the Limpopo Belt, South Africa

The Southern Marginal Zone of the Limpopo Belt in South Africa is characterised by a granulite and retrograde hydrated granulite terrane. The Southern Marginal Zone is, therefore, perfectly suitable to study fluids during and after granulite facies metamorphism by means of fluid inclusions and equilibrium calculations. Isolated and clustered high-salinity aqueous and CO₂(-CH₄) fluid inclusions within quartz inclusions in garnet in metapelites demonstrate that these immiscible low H₂O activity fluids were present under peak metamorphic conditions (800-850 °C, 7.5-8.5 kbar). The absence of widespread high-temperature metasomatic alteration indicates that the brine fluid was probably only locally present in small quantities. Thermocalc calculations demonstrate that the peak metamorphic mineral assemblage in mafic granulites was in equilibrium with a fluid with a low H₂O activity (0.2-0.3). The absence of water in CO₂-rich fluid inclusions is due to either observation difficulties or selective water leakage. The density of CO₂ inclusions in trails suggests a retrograde P-T path dominated by decompression at T<600 °C. Re-evaluation of previously published data demonstrates that retrograde hydration of the granulites at 600 °C occurred in the presence of H₂O and CO₂-rich fluids under P-T conditions of 5-6 kbar and ~600 °C. The different compositions of the hydrating fluid suggest more than one fluid source.     

Anatexis and fluid regime of the deep continental crust: New clues from melt and fluid inclusions in metapelitic migmatites from Ivrea Zone (NW Italy)

We investigate the inclusions hosted in peritectic garnet from metapelitic migmatites of the Kinzigite Formation (Ivrea Zone, NW Italy) to evaluate the starting composition of the anatectic melt and fluid regime during anatexis throughout the upper amphibolite facies, transition, and granulite facies zones. Inclusions have negative crystal shapes, sizes from 2 to 10 μm and are regularly distributed in the core of the garnet. Microstructural and micro‐Raman investigations indicate the presence of two types of inclusions: crystallized silicate melt inclusions (i.e., nanogranitoids, NI), and fluid inclusions (FI). Microstructural evidence suggests that FI and NI coexist in the same cluster and are primary (i.e., were trapped simultaneously during garnet growth). FI have similar compositions in the three zones and comprise variable proportions of CO₂, CH₄, and N₂, commonly with siderite, pyrophyllite, and kaolinite, suggesting a COHN composition of the trapped fluid. The mineral assemblage in the NI contains K‐feldspar, plagioclase, quartz, biotite, muscovite, chlorite, graphite and, rarely, calcite. Polymorphs such as kumdykolite, cristobalite, tridymite, and less commonly kokchetavite, were also found. Rehomogenized NI from the different zones show that all the melts are leucogranitic but have slightly different compositions. In samples from the upper amphibolite facies, melts are less mafic (FeO + MgO = 2.0–3.4 wt%), contain 860–1700 ppm CO₂ and reach the highest H₂O contents (6.5–10 wt%). In the transition zone melts have intermediate H₂O (4.8–8.5 wt%), CO₂ (457–1534 ppm) and maficity (FeO + MgO = 2.3–3.9 wt%). In contrast, melts at granulite facies reach highest CaO, FeO + MgO (3.2–4.7 wt%), and CO₂ (up to 2,400 ppm), with H₂O contents comparable (5.4–8.3 wt%) to the other two zones. Our results represent the first clear evidence for carbonic fluid‐present melting in the Ivrea Zone. Anatexis of metapelites occurred through muscovite and biotite breakdown melting in the presence of a COH fluid, in a situation of fluid–melt immiscibility. The fluid is assumed to have been internally derived, produced initially by devolatilization of hydrous silicates in the graphitic protolith, then as a result of oxidation of carbon by consumption of Fe³⁺‐bearing biotite during melting. Variations in the compositions of the melts are interpreted to result from higher T of melting. The H₂O contents of the melts throughout the three zones are higher than usually assumed for initial H₂O contents of anatectic melts. The CO₂ contents are highest at granulite facies, and show that carbon‐contents of crustal magmas are not negligible at high T. The activity of H₂O of the fluid dissolved in granitic melts decreases with increasing metamorphic grade. Carbonic fluid‐present melting of the deep continental crust represents, together with hydrate‐breakdown melting reactions, an important process in the origin of crustal anatectic granitoids.     

Role of H2O in the formation of garnet coronas during near‐isobaric cooling of mafic granulites: the Tasiusarsuaq terrane,southern West Greenland

The Mesoarchaean Tasiusarsuaq terrane of southern West Greenland consists of Tonalite–trondhjemite–granodiorite gneisses and, locally, polymetamorphic mafic and ultramafic rocks. The terrane experienced medium‐pressure granulite facies conditions during M_1A in the Neoarchean, resulting in the development of two‐pyroxene melanosome assemblages in mafic granulites containing garnet‐bearing leucosome. Reworking of these rocks during retrogression introduced garnet to the melanosome in the form of overgrowths, coronas and grain necklaces that separate the mafic minerals from plagioclase. NCFMASHTO pseudosection modelling constrains the peak metamorphism during M_1A to ～850 °C and 7.5 kbar at fluid‐saturated conditions. Following M_1A, the rocks retained their M_1A H₂O content and became fluid‐undersaturated as they underwent near‐isobaric cooling to ～700 °C and 6.5–7 kbar, prior to reworking during M_1B. These low H₂O contents allowed for the formation of garnet overgrowths and coronas during M_1B. The stability of garnet is greatly increased to lower pressure and temperature in fluid‐absent, fluid‐undersaturated mafic rocks, indicating that fluid and melt loss during initial granulite facies metamorphism is essential for the introduction of garnet, and the formation of garnet coronas, during retrogression. The occurrence of garnet coronas is consistent with, but not unique to, near‐isobaric cooling paths.     

Fluid compositions and local fluid buffering during the retrograde metamorphism of Al-bearing dolomitic calc-silicate granulites in the Limpopo Central Zone,southern Africa

Calc-silicate granulites were examined to evaluate the fluid composition and retrograde metamorphic conditions in the Central Zone of the Limpopo Belt, southern Africa. Quartz deficient assemblages are characterized by minerals such as diopside, forsterite, spinel and/or magnesiohornblende and tremolite in the presence of calcite and dolomite. Although the granulites are Al-poor (Al₂O₃ is less than or equal to 1.0 wt.%) and dolomitic in composition, they include Al-bearing phases. Phase analyses for the assemblages in the two model systems CaO–MgO–SiO₂–H₂O–CO₂ and CaO–MgO–SiO₂–Al₂O₃–H₂O–CO₂ provide constraints on fluid compositions in the granulite facies and retrograde metamorphisms in the Limpopo Central Zone. In the presence of amphiboles, isobaric T–X(CO₂) phase relations suggest that high X(CO₂) conditions were established in the calc-silicate rocks of present study. The phase relations with tschermakitic amphiboles at 0.35 GPa restrict diopside-spinel occurrences in the presence of calcite, dolomite and forsterite within very-high X(CO₂) with low a(H₂O). The fluid compositions, X(CO₂), were effectively buffered by the mineral assemblages during granulite facies metamorphism to subsequent decompression and cooling stages. The presence or absence of retrograde magnesiohornblende and tremolite appeared to be controlled not only by infiltration of H₂O-rich fluid during retrograde metamorphism but also Al content in the local bulk rock compositions. The presence of the two-amphibole phases shows that the fluid compositions were locally buffered in the Al-bearing dolomitic granulites. Comparing the calculated X(CO₂) values in the present study area and in the Alldays area, a difference of retrograde hydration effects is observed.     

Fluid inclusions in Adirondack granulites: Implications for the retrograde P-T path

Investigation of fluid inclusions in granitic and cale-silicate gneisses from the Adirondack Mountains, New York, has revealed the presence of various types, including: (1) CO₂-rich, (2) mixed H₂O–CO₂±salt and (3) aqueous inclusions with no visible CO₂. Many, if not all, of these inclusions were trapped or modified after the peak of granulite facies metamorphism, as shown by textural relations or by the lack of agreement between the composition of the fluids found in some inclusions and the composition of the peak-metamorphic fluid as estimated from mineral equilibria. Many fluid inclusions record conditions attained during retrograde cooling and uplift, with minimum pressures and temperatures of 2 to 3 kbar and 200 to 300°C. The temperatures and pressures derived from the investigation of these inclusions constrain the retrograde P-T path, and the results indicate that a period of cooling with little or no decompression.     

Fluid‐fluxed melting and melt loss in a syntectonic contact metamorphic aureole from the Variscan eastern Pyrenees

Open‐system behaviour through fluid influx and melt loss can produce a variety of migmatite morphologies and mineral assemblages from the same protolith composition. This is shown by different types of granulite facies migmatite from the contact aureole of the Ceret gabbro–diorite stock in the Roc de Frausa Massif (eastern Pyrenees). Patch, stromatic and schollen migmatites are identified in the inner contact aureole, whereas schollen migmatites and residual melanosomes are found as xenoliths inside the gabbro–diorite. Patch and schollen migmatites record D1 and D2 structures in folded melanosome and mostly preserve the high‐T D2 in granular or weakly foliated leucosome. Stromatic migmatites and residual melanosomes only preserve D2. The assemblage quartz–garnet–biotite–sillimanite–cordierite±K‐feldspar–plagioclase is present in patch and schollen migmatites, whereas stromatic migmatites and residual melanosomes contain a sub‐assemblage with no sillimanite and/or K‐feldspar. A decrease in X _Fe (molar Fe/(Fe + Mg)) in garnet, biotite and cordierite is observed from patch migmatites through schollen and stromatic migmatites to residual melanosomes. Whole‐rock compositions of patch, schollen and stromatic migmatites are similar to those of non‐migmatitic rocks from the surrounding area. These metasedimentary rocks are interpreted as the protoliths of the migmatites. A decrease in the silica content of migmatites from 63 to 40 wt% SiO₂ is accompanied by an increase in Al₂O₃ and MgO+FeO and by a depletion in alkalis. Thermodynamic modelling in the NCKFMASHTO system for the different types of migmatite provides peak metamorphic conditions ~7–8 kbar and 840 °C. A nearly isothermal decompression history down to 5.5 kbar was followed by isobaric cooling from 840 °C through 690 °C to lower temperatures. The preservation of granulite facies assemblages and the variation in mineral assemblages and chemical composition can be modelled by ongoing H₂O‐fluxed melting accompanied by melt loss. The fluids were probably released by the crystallizing gabbro–diorite, infiltrating the metasedimentary rocks and fluxing melting. Release of fluids and melt loss were probably favoured by coeval deformation (D2). The amount of melt remaining in the system varied considerably among the different types of migmatite. The whole‐rock compositions of the samples, the modelled compositions of melts at the solidus at 5.5 kbar and the residues show a good correlation.     

P-T-X parameters of metamorphogene and hydrothermal fluids,isotopy and age of the Bogunai gold deposit,southern Yenisei Ridge (Russia)

Fluid inclusions in quartz, sulfides from quartz veins, and quartz, garnet, plagioclase, and orthoclase from granulites of the Bogunai gold deposit located in the granulites of the Angara-Kan block of the Yenisei Ridge were studied by thermobarometry, gas chromatography, chromato-mass-spectrometry, Raman spectroscopy, and mass spectrometry with inductively coupled plasma. The formation temperatures (850-950 °C) and pressures (8.5-9.0 kbar) of minerals of the granulite metamorphic facies are much higher than the crystallization temperatures (220-420 °C) and pressures (0.1-1.6 kbar) of gold-quartz veins of the Bogunai deposit. These veins formed with the participation of H₂O-CO₂-hydrocarbon fluids with a salt (predominantly MgCl₂) concentration of 2-19 wt.% NaCl equiv. The gas phase of fluid inclusions from quartz, pyrite, chalcopyrite, galena, and sphalerite contains not only H₂O, CO₂, CH₄, and N₂ but also the first found compounds of sulfur (CS₂, O₂S, COS, C₂H6S₂) and nitrogen (C3H₇N, C3H₇NO, C₄H8N₂O) and numerous hydrocarbons of different classes (paraffins, arenes, naphthenes, alcohols, aldehydes, ketones, carbonic acids, and furans). The age of the Krasnoyarsk mineralized zone, one of the sites of the Bogunai deposit, is 466 ± 3.2-461.6 ± 3.1 Ma, which is almost 1400 Ma younger than the age of granulite metamorphism and 255 Ma younger than the age of diaphthoresis but is close to the age of the Lower Kan granitoid pluton (455.7 ± 3.4 Ma). The sulfur isotope ratios (5³⁴S) of sulfides (pyrite, chalcopyrite, sphalerite, and galena) are close to the mantle values, 0.8 to 3.5%c, and are in the range of the granitoid values, which indicates the crustal source of the fluid sulfur. Gold of the Bogunai deposit accumulated with the participation of H₂O-CO₂-hydrocarbon fluids generated both in deep-fault zones and in granitoid intrusions.     

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.