Application of mineral equilibria modeling to constrain T and X CO2 conditions during the evolution of the Magdala gold deposit, Stawell, Victoria, Australia

Mineral equilibria modeling involving solid solution calculations has been combined with mineral assemblage information from the alteration zones associated with gold mineralization to determine the T and X _CO2 conditions for the formation of the Magdala gold deposit at Stawell, Victoria, Australia. Economic gold mineralization is primarily hosted within the stilpnomelane alteration zone of the Stawell Facies that is adjacent to the Magdala Basalt. Evolution of the Magdala gold deposit involved at least three fluid infiltration events: (1) a CO₂-bearing fluid during the D₂ deformation event produced carbonate spots throughout the chlorite zone; (2) a CO₂–S–K-bearing fluid, accompanied the D_3–4ab deformation and produced a muscovite zone and siderite rims on ankerite; and (3) a CO₂–K–S–Au-bearing fluid during the D_4c deformation event produced the stilpnomelane zone of the Stawell Facies, the proximal and distal alteration zones within the Magdala Basalt, and the main economic gold mineralization. Mineral equilibria modeling constrains the temperature of formation of the Magdala deposit to T = 345–390°C at 3kbar, substantially lower than indicated by other previous classical thermobarometry methods. Furthermore, this method has allowed the characterization of the mineralizing fluid and constrained its composition to X _CO2 < 0.08 at 3kbar. The timing and composition of the mineralizing fluids are similar to that of metamorphic fluid generated from devolatilization of a greenstone pile with peak of metamorphism occurring earlier and at deeper levels in the crust.     

A mineral equilibria study of the hydrothermal alteration in mafic greenschist facies rocks at Kalgoorlie, Western Australia

The influx of a H₂O–CO₂‐dominated fluid into actinolite‐bearing metabasic rocks during greenschist facies metamorphism in the Kalgoorlie area of Western Australia resulted in a zoned alteration halo around inferred fluid conduits that contain gold mineralisation. The alteration halo is divided into two outer zones, the chlorite zone and the carbonate zone, and an inner pyrite zone adjacent to the inferred fluid conduits. Reaction between the fluid and the protolith resulted in the breakdown of actinolite and the development of chlorite, dolomite, calcite and siderite. In addition, rocks in the pyrite zone developed muscovite‐bearing assemblages as a consequence of the introduction of potassium by the fluid. Mineral equilibria calculations undertaken using the computer software thermocalc in the model system Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–CO₂ show that mineral assemblages in the outer zones of the alteration halo are consistent with equilibrium of the protoliths with a fluid of composition X_CO2 = CO₂/(CO₂ + H₂O) = 0.1–0.25 for temperatures of 315–320 °C. The inner zone of the alteration halo reflect equilibrium with a fluid of composition X_CO2≈ 0.25. Fluid‐rock buffering calculations show that the alteration halo is consistent with interaction with a single fluid composition and that the zoned structure of the halo reflects the volume of this fluid with which the rocks reacted. This fluid is likely to have also been the one responsible for the gold mineralisation at Kalgoorlie.     

Coexistence of garnet blueschist and eclogite in South Tianshan,NW China: dependence of P–T evolution and bulk‐rock composition

Coexisting garnet blueschist and eclogite from the Chinese South Tianshan high‐pressure (HP)–ultrahigh‐pressure (UHP) belt consist of similar mineral assemblages involving garnet, omphacite, glaucophane, epidote, phengite, rutile/sphene, quartz and hornblendic amphibole with or without paragonite. Eclogite assemblages generally contain omphacite >50 vol.% and a small amount of glaucophane (<5 vol.%), whereas blueschist assemblages have glaucophane over 30 vol.% with a small amount of omphacite which is even absent in the matrix. The coexisting blueschist and eclogite show dramatic differences in the bulk‐rock compositions with higher X(CaO) [=CaO/(CaO + MgO + FeO_total + MnO + Na₂O)] (0.33–0.48) and lower A/CNK [=Al₂O₃/(CaO + Na₂O + K₂O)] (0.35–0.56) in eclogite, but with lower X(CaO) (0.09–0.30) and higher A/CNK (0.65–1.28) in garnet blueschist. Garnet in both types of rocks has similar compositions and exhibits core–rim zoning with increasing grossular and pyrope contents. Petrographic observations and phase equilibria modelling with pseudosections calculated using thermocalc in the NCKMnFMASHO system for the coexisting garnet blueschist and eclogite samples suggest that the two rock types share similar P–T evolutional histories involving a decompression with heating from the P_max to the T_max stage and a post‐T_max decompression with slightly cooling stage, and similar P–T conditions at the T_max stage. The post‐T_max decompression is responsible for lawsonite decomposition, which results in epidote growth, glaucophane increase and omphacite decrease in the blueschist, or in an overprinting of the eclogitic assemblage by a blueschist assemblage. Calculated P–X(CaO), P–A/CNK and P–X(CO₂) pseudosections indicate that blueschist assemblages are favoured in rocks with lower X(CaO) (<0.28) and higher A/CNK (>0.75) or fluid composition with higher X(CO₂) (>0.15), but eclogite assemblages preferentially occur in rocks with higher X(CaO) and lower A/CNK or fluid composition with lower X(CO₂). Moreover, phase modelling suggests that the coexistence of blueschist and eclogite depends substantially on P–T conditions, which would commonly occur in medium temperatures of 500–590 °C under pressures of ~17–22 kbar. The modelling results are in good accordance with the measured bulk‐rock compositions and modelled temperature results of the coexisting garnet blueschist and eclogite from the South Tianshan HP–UHP belt.     

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     

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.     

Metamorphism in Archaean greenstone belts: calculated fluid compositions and implications for gold mineralization

An inescapable consequence of the metamorphism of greenstone belt sequences is the release of a large volume of metamorphic fluid of low salinity with chemical characteristics controlled by the mineral assemblages involved in the devolatilization reactions. For mafic and ultramafic sequences, the composition of fluids released at upper greenschist to lower amphibolite facies conditions for the necessary relatively hot geotherm corresponds to those inferred for greenstone gold deposits (X_CO2= 0.2–0.3). This result follows from the calculation of mineral equilibria in the model system CaO–MgO–FeO–Al₂O₃–SiO₂–H₂O–CO₂, using a new, expanded, internally consistent dataset. Greenstone metamorphism cannot have involved much crustal over-thickening, because very shallow levels of greenstone belts are preserved. Such orogeny can be accounted for if compressive deformation of the crust is accompanied by thinning of the mantle lithosphere. In this case, the observed metamorphism, which was contemporaneous with deformation, is of the low-P high-T type. For this type of metamorphism, the metamorphic peak should have occurred earlier at deeper levels in the crust; i.e. the piezothermal array should be of the ‘deeper-earlier’type. However, at shallow crustal levels, the piezothermal array is likely to have been of ‘deeper-later’type, as a consequence of erosion. Thus, while the lower crust reached maximum temperatures, and partially melted to produce the observed granites, mid-crustal levels were releasing fluids prograde into shallow crustal levels that were already retrograde. We propose that these fluids are responsible for the gold mineralization. Thus, the contemporaneity of igneous activity and gold mineralization is a natural consequence of the thermal evolution, and does not mean that the mineralization has to be a consequence of igneous processes. Upward migration of metamorphic fluid, via appropriate structurally controlled pathways, will bring the fluid into contact with mineral assemblages that have equilibrated with a fluid with significantly lower X_CO2. These assemblages are therefore grossly out of equilibrium with the fluid. In the case of infiltrated metabasic rocks, intense carbonation and sulphidation is predicted. If, as seems reasonable, gold is mobilized by the fluid generated by devolatilization, then the combination of processes proposed, most of which are an inevitable consequence of the metamorphism, leads to the formation of greenstone gold deposits predominantly from metamorphic fluids.     

Phase equilibria modelling of retrograde amphibole and clinozoisite in mafic eclogite from the Tso Morari massif,northwest India: constraining the P–T–M(H2O) conditions of exhumation

Phase equilibria modelling of post‐peak metamorphic mineral assemblages in (ultra)high‐P mafic eclogite from the Tso Morari massif, Ladakh Himalaya, northwest India, has provided new insights into the potential behaviour and source of metamorphic fluid during exhumation, and constrained the P–T conditions of hydration. A series of P–M(H₂O) pseudosections constructed in the Na₂O–CaO–K₂O–FeO–MgO–Al₂O₃–SiO₂–H₂O–TiO₂–O (NCKFMASHTO) system show that a number of petrographically distinct hydration episodes occurred during exhumation from peak P–T conditions (~640 °C, 27–28 kbar), resulting in the formation of abundant compositionally zoned amphibole and minor clinozoisite poikiloblasts at the expense of a peak assemblage dominated by garnet and omphacite. Initial hydration is interpreted to have occurred as a result of the destabilization of talc following isothermal decompression to ~23 kbar, which led to the formation of barroisite–winchite amphibole core domains. An episode of fluid infiltration from an external source at ~19 kbar, with or without syn‐decompressional cooling to ~560 °C, resulted in further barroisitic–winchitic amphibole growth, followed by the formation of clinozoisite poikiloblasts. Continued buoyancy‐driven exhumation to the base of the lower crust is constrained to have taken place with no additional fluid input. A final hydration event is characterized by the formation of magnesiohornblende rims on the barroisite–winchite cores, with the former interpreted to have formed during later prograde overprinting in the middle crust associated with the final stages of exhumation. Notably, the vast majority of externally sourced H₂O, comprising just over half of the current bulk rock fluid content, was added during this later hydration event. In a middle crustal setting, this is interpreted as the result of devolatilization reactions occurring in migmatitic host orthogneiss and/or metasedimentary units, or following the crystallization of partial melt.     

Devolatilization of metabasic rocks during greenschist–amphibolite facies metamorphism

The production of large volumes of fluid from metabasic rocks, particularly in greenstone terranes heated across the greenschist–amphibolite facies transition, is widely accepted yet poorly characterized. The presence of carbonate minerals in such rocks, commonly as a consequence of sea‐floor alteration, has a strong influence, via fluid‐rock buffering, on the mineral equilibria evolution and fluid composition. Mineral equilibria modelling of metabasic rocks in the system Na₂O‐CaO‐FeO‐MgO‐Al₂O₃‐SiO₂‐CO₂‐H₂O (NCaFMASCH) is used to constrain the stability of common metabasic assemblages. Calculated buffering paths on T–X_CO2 pseudosections, illustrate the evolution of greenstone terranes during heating across the greenschist‐amphibolite transition. The calculated paths constrain the volume and the composition of fluid produced by devolatilization and buffering. The calculated amount and composition of fluid produced are shown to vary depending on P–T conditions, the proportion of carbonate minerals and the X_CO2 of the rocks prior to prograde metamorphism. In rocks with an initially low proportion of carbonate minerals, the greenschist to amphibolite facies transition is the primary period of fluid production, producing fluid with a low X_CO2. Rocks with greater initial proportions of carbonate minerals experience a second fluid production event at temperatures above the greenschist to amphibolite facies transition, producing a more CO₂‐rich fluid (X_CO2 = 0.2–0.3). Rocks may achieve these higher proportions of carbonate minerals either via more extensive seafloor alteration or via infiltration of fluids. Fluid produced via devolatilization of rocks at deeper crustal levels may infiltrate and react with overlying lower temperature rocks, resulting in external buffering of those rocks to higher X_CO2 and proportions of carbonate minerals. Subsequent heating and devolatilization of these overlying rocks results in buffering paths that produce large proportions of fluid at X_CO2 = 0.2–0.3. The production of fluid of this composition is of importance to models of gold transport in Archean greenstone gold deposits occurring within extensive fluid alteration haloes, as these haloes represent the influx of fluid of X_CO2 = 0.2–0.3 into the upper crust.     

Internally consistent data for sulphur‐bearing phases and application to the construction of pseudosections for mafic greenschist facies rocks in Na2O–CaO–K2O–FeO–MgO–Al2O3–SiO2–CO2–O–S–H2O

The Holland and Powell internally consistent data set version 5.5 has been augmented to include pyrite, troilite, trov (Fe_0.875S), anhydrite, H₂S, elemental S and S₂ gas. Phase changes in troilite and pyrrhotite are modelled with a combination of multiple end‐members and a Landau tricritical model. Pyrrhotite is modelled as a solid solution between hypothetical end‐member troilite (trot) and Fe_0.875S (trov); observed activity–composition relationships fit well to a symmetric formalism model with a value for w_trot?trov of ?3.19 kJ mol^?1. The hypothetical end‐member approach is required to compensate for iron distribution irregularities in compositions close to troilite. Mixing in fluids is described with the van Laar asymmetric formalism model with a_ij values for H₂O–H₂S, H₂S–CH₄ and H₂S–CO₂ of 6.5, 4.15 and 0.045 kJ mol^?1 respectively. The derived data set is statistically acceptable and replicates the input data and data from experiments that were not included in the initial regression. The new data set is applied to the construction of pseudosections for the bulk composition of mafic greenschist facies rocks from the Golden Mile, Kalgoorlie, Western Australia. The sequence of mineral assemblages is replicated successfully, with observed assemblages predicted to be stable at X(CO₂) increasing with increasing degree of hydrothermal alteration. Results are compatible with those of previous work. Assemblages are insensitive to the S bulk content at S contents of less than 1 wt%, which means that volatilization of S‐bearing fluids and sulphidation are unlikely to have had major effects on the stable mineral assemblage in less metasomatized rocks. The sequence of sulphide and oxide phases is predicted successfully and there is potential to use these phases qualitatively for geobarometry. Increases in X(CO₂) stabilized, in turn, pyrite–magnetite, pyrite–hematite and anhydrite–pyrite. Magnetite–pyrrhotite is predicted at temperatures greater than 410 °C. The prediction of a variety of sulphide and oxide phases in a rock of fixed bulk composition as a function of changes in fluid composition and temperature is of particular interest because it has been proposed that such a variation in phase assemblage is produced by the infiltration of multiple fluids with contrasting redox state. The work presented here shows that this need not be the case.     

Formation of the Campbell-Red Lake gold deposit by H2O-poor, CO2-dominated fluids

The Campbell-Red Lake gold deposit in the Red Lake greenstone belt, with a total of approximately 840 t of gold (past production + reserves) and an average grade of 21 g/t Au, is one of the largest and richest Archean gold deposits in Canada. Gold mineralization is mainly associated with silicification and arsenopyrite that replace carbonate veins, breccias and wallrock selvages. The carbonate veins and breccias, which are composed of ankerite ± quartz and characterized by crustiform–cockade textures, were formed before and/or in the early stage of penetrative ductile deformation, whereas silicification, arsenopyrite replacement and gold mineralization were coeval with deformation. Microthermometry and laser Raman spectroscopy indicate that fluid inclusions in ankerite and associated quartz (Q1) and main ore-stage quartz (Q2) are predominantly carbonic, composed mainly of CO₂, with minor CH₄ and N₂. Aqueous and aqueous–carbonic inclusions are extremely rare in both ankerite and quartz. H₂O was not detected by laser Raman spectroscopic analyses of individual carbonic inclusions and by gas chromatographic analyses of bulk samples of ankerite and main ore-stage quartz (Q2). Fluid inclusions in post-mineralization quartz (Q3) are also mainly carbonic, but proportions of aqueous and aqueous–carbonic inclusions are present. Trace amounts of H₂S were detected by laser Raman spectroscopy in some carbonic inclusions in Q2 and Q3, and by gas chromatographic analyses of bulk samples of ankerite and Q2. ³He/⁴He ratios of bulk fluid inclusions range from 0.008 to 0.016 Ra in samples of arsenopyrite and gold. Homogenization temperatures (T _h–CO₂) of carbonic inclusions are highly variable (from −4.1 to +30.4°C; mostly to liquid, some to vapor), but the spreads within individual fluid inclusion assemblages (FIAs) are relatively small (within 0.5 to 10.3°C). Carbonic inclusions occur both in FIAs with narrow T _h–CO₂ ranges and in those with relatively large T _h–CO₂ variations. The predominance of carbonic fluid inclusions has been previously reported in a few other gold deposits, and its significance for gold metallogeny has been debated. Some authors have proposed that formation of the carbonic fluid inclusions and their predominance is due to post-trapping leakage of water from aqueous–carbonic inclusions (H₂O leakage model), whereas others have proposed that they reflect preferential trapping of the CO₂-dominated vapor in an immiscible aqueous–carbonic mixture (fluid unmixing model), or represent an unusually H₂O-poor, CO₂-dominated fluid (single carbonic fluid model). Based on the FIA analysis reported in this study, we argue that although post-trapping modifications and host mineral deformation may have altered the fluid inclusions in varying degrees, these processes were not solely responsible for the formation of the carbonic inclusions. The single carbonic fluid model best explains the extreme rarity of aqueous inclusions but lacks the support of experimental data that might indicate the viability of significant transport of silica and gold in a carbonic fluid. In contrast, the weakness of the unmixing model is that it lacks unequivocal petrographic evidence of phase separation. If the unmixing model were to be applied, the fluid prior to unmixing would have to be much more enriched in carbonic species and poorer in water than in most orogenic gold deposits in order to explain the predominance of carbonic inclusions. The H₂O-poor, CO₂-dominated fluid may have been the product of high-grade metamorphism or early degassing of magmatic intrusions, or could have resulted from the accumulation of vapor produced by phase separation external to the site of mineralization.Geological Survey of Canada contribution 2004383.     

Metamorphic evolution of relict lawsonite‐bearing eclogites from the (U) HP metamorphic belt in the Chinese southwestern Tianshan

In the Chinese southwestern Tianshan (U)HP belt, former lawsonite presence has been predicted for many (U)HP metamorphic eclogites, but only a very few lawsonite grains have been found so far. We discovered armoured lawsonite relicts included in quartz, which, on its part, is enclosed in porphyroblastic garnet in an epidote eclogite H711‐14 and a paragonite eclogite H711‐29. H711‐14 is mainly composed of garnet, omphacite, epidote and titanite, with minor quartz, paragonite and secondary barroisite and glaucophane. Coarse‐grained titanite occasionally occurs in millimetre‐wide veins in equilibrium with epidote and omphacite, and relict rutile is only preserved as inclusions in matrix titanite and garnet. H711‐29 shows the mineral assemblage of garnet, omphacite, glaucophane, paragonite, quartz, dolomite, rutile and minor epidote. Dolomite and rutile are commonly rimed by secondary calcite and titanite respectively. Porphyroblastic garnet in both eclogites is compositionally zoned and exhibits an inclusion‐rich core overgrown by an inclusion‐poor rim. Phase equilibria modelling predicts that garnet cores formed at the P‐peak (490–505 °C and 23–25.5 kbar) and coexisted with the lawsonite eclogite facies assemblage of omphacite + glaucophane + lawsonite + quartz. Garnet rims (550–570 °C and ~20 kbar) grew subsequently during a post‐peak epidote eclogite facies metamorphism and coexisted with omphacite + quartz ± glaucophane ± epidote ± paragonite. The results confirm the former presence of a cold subduction zone environment in the Chinese southwestern Tianshan. The P–T evolution of the eclogites is characterized by a clockwise P–T path with a heating stage during early exhumation (thermal relaxation). The preservation of lawsonite in these eclogites is attributed to isolation from the matrix by quartz and rigid garnet, which should be considered as a new type of lawsonite preservation in eclogites. The complete rutile–titanite transition in H711‐14 took place in the epidote eclogite facies stage in the presence of an extremely CO₂‐poor fluid with X(CO₂) [CO₂/(CO₂ + H₂O) in the fluid] <<0.008. In contrast, the incomplete rutile–titanite transition in H711‐29 may have occurred after the epidote eclogite facies stage and the presence of dolomite reflects a higher X(CO₂) (>0.01) in the coexisting fluid at the epidote eclogite facies stage.     

Fluid evolution in base‐metal sulphide mineral deposits in the metamorphic basement rocks of southwest Scotland and Northern Ireland

The Dalradian and Ordovician–Silurian metamorphic basement rocks of southwest Scotland and Northern Ireland host a number of base‐metal sulphide‐bearing vein deposits associated with kilometre‐scale fracture systems. Fluid inclusion microthermometric analysis reveals two distinct fluid types are present at more than half of these deposits. The first is an H₂O–CO₂–salt fluid, which was probably derived from devolatilization reactions during Caledonian metamorphism. This stage of mineralization in Dalradian rocks was associated with base‐metal deposition and occurred at temperatures between 220 and 360°C and pressures of between 1.6 and 1.9 kbar. Caledonian mineralization in Ordovician–Silurian metamorphic rocks occurred at temperatures between 300 and 360°C and pressures between 0.6 and 1.9 kbar. A later, probably Carboniferous, stage of mineralization was associated with base‐metal sulphide deposition and involved a low to moderate temperature (T_h 70 to 240°C), low to moderate salinity (0 to 20 wt% NaCl eq.), H₂O–salt fluid. The presence of both fluids at many of the deposits shows that the fractures hosting the deposits acted as long‐term controls for fluid migration and the location of Caledonian metalliferous fluids as well as Carboniferous metalliferous fluids. Copyright © 2004 John Wiley & Sons, Ltd.     

Stable staurolite–cordierite assemblages in K‐poor metapelitic schists in Aston and Hospitalet gneiss domes of the central Pyrenees (France,Andorra)

Staurolite–cordierite assemblages are common in mica schists of the Aston and Hospitalet gneiss domes of the central Axial Zone, Pyrenees (France, Andorra). Within a 200 m wide zone, staurolite, cordierite and andalusite porphyroblasts contain inclusion trails that preserve the same stage of development of a crenulation cleavage, strongly suggesting that all three phases are contemporaneous. Their syntectonic growth occurred during a short period at the beginning of the formation of the dominant schistosity (S₂) of the domes. Staurolite and cordierite touching each other further indicates an equilibrium relationship. Whole‐rock analyses show that some staurolite–cordierite schists are depleted in K₂O compared to post‐Archean shales (PAAS) and amphibolite facies pelites. Analysis of the st‐crd paragenesis in K‐poor schists without muscovite using KFMASH and MnNCKFMASH petrogentic grids, pseudosections and AFM compatibility diagrams predicts stable conditions at pressures of ~3.5 kbar at 575 °C. For metapelites with intermediate X_Mg values (0.7 >  X_Mg >0.48) a ‘muscovite‐out window’ exists from 550–650 °C at 3.5 kbar in the KFMASH system. Conventional thermobarometry (GB‐GASP, AvT‐AvP) and petrogenetic grids show an isobaric P–T path to peak temperatures of ~650 °C, supported by the presence of sillimanite‐K‐feldspar gneiss and migmatites. LP‐HT metamorphism in the Aston dome is related to early Carboniferous (c. 339 Ma) granitic intrusions into the dome core. As metamorphism is directly linked with the formation of the main S₂ schistosity, the temporal relations demonstrated in this study conflict with previous studies which constrained LP‐HT metamorphism and the development of flat‐lying schistosity to the late Carboniferous (315–305 Ma) – at least in the eastern Axial Zone.     

A curious case of agreement between conventional thermobarometry and phase equilibria modelling in granulites: New constraints on P–T estimates in the Antarctica segment of the Musgrave–Albany–Fraser–Wilkes Orogen

The Windmill Islands region in Wilkes Land, east Antarctica, preserves granulite facies metamorphic mineral assemblages that yield seemingly comparable P–T estimates from conventional thermobarometry and mineral equilibria modelling. This is uncommon in granulite facies terranes, where conventional thermobarometry and phase equilibria modelling generally produce conflicting P–T estimates because peak mineral compositions tend to be modified by retrograde diffusion processes. In situ U–Pb monazite geochronology and calculated metamorphic phase diagrams show that the Windmill Islands experienced two phases of high thermal gradient metamorphism during the Mesoproterozoic. The first phase of metamorphism is recorded by monazite ages in two widely separated samples and occurred at c. 1,305 Ma. This event was regional in extent, involved crustally derived magmatism and reached conditions of ~3.2–5 kbar and 690–770°C corresponding to very high thermal gradients of >150°C/kbar. The elevated thermal regime is interpreted to reflect a period of extension or increased extension in a back‐arc setting that existed prior to c. 1,330 Ma. The first metamorphic event was overprinted by granulite facies metamorphism at c. 1,180 Ma that was coeval with the intrusion of charnockite. This event involved peak temperatures of ~840–850°C and pressures of ~4–5 kbar. A phase of granitic magmatism at c. 1,250–1,210 Ma, prior to the intrusion of the charnockite, is interpreted to reflect a phase of compression within an overall back‐arc setting. Existing conventional thermobarometry suggests conditions of ~4 kbar and 750°C for M₁ and 4–7 kbar and 750–900°C for M₂. The apparent similarities between the phase equilibria modelling and existing conventional thermobarometry may suggest either that the terrane cooled relatively quickly, or that the P–T ranges obtained from conventional thermobarometry are sufficiently imprecise that they cover the range of P–T conditions obtained in this study. However, without phase equilibria modelling, the veracity of existing conventional P–T estimates cannot be evaluated. The calculated phase diagrams from this study allow the direct comparison of P–T conditions in the Windmill Islands with phase equilibria models from other regions in the Musgrave–Albany–Fraser–Wilkes Orogen. This shows that the metamorphic evolution of the Wilkes Land region is very similar to that of the eastern Albany–Fraser Orogen and Musgrave Province in Australia, and further demonstrates the remarkable consistency in the timing of metamorphism and the thermal gradients along the ~5,000 km strike length of this system.     

Polymetamorphism in garnet micaschists of the Saualpe Eclogite Unit (Eastern Alps,Austria), resolved by automated SEM methods and EMP–Th–U–Pb monazite dating

Polymetamorphic garnet micaschists from the Austroalpine Saualpe Eclogite Unit (Kärnten, Austria, Eastern Alps) display complex microstructural and mineral–chemical relationships. Automated scanning electron microscopy routines with energy dispersive X‐ray (EDX) spectral mapping were applied for monazite detection and garnet mineral–chemical characterization. When the Fe, Mg, Mn and Ca element wt% compositions are used as generic labels for garnet EDX spectra, complex zonations and porphyroblast generations can be resolved in complete thin sections for selective electron‐microprobe analyses. Two garnet porphyroblast generations and diverse monazite age populations have been revealed in low‐Ca and high‐Al‐metapelites. Garnet 1 has decreasing Mn, constant Ca and significantly increasing Mg from cores to rims. Geothermobarometry of garnet 1 assemblages signals a crystallization along a M1 prograde metamorphism at ~650 °C/6–8 kbar. Sporadic monazite 1 crystallization started at c. 320 Ma. Subsequent pervasive 300–250 Ma high‐Y and high‐Gd monazite 1 formation during decompression coincided with the intrusion of Permian and Early Triassic pegmatites. Monazite 1 crystallized along the margin of garnet 1. Coronas of apatite and allanite around the large 320–250 Ma monazite signal a retrogressive stage. These microstructures suggest a Carboniferous‐to‐Early‐Permian age for the prograde M1 event with garnet 1. Such a M1 event at an intermediate‐P/T gradient has not yet been described from the Saualpe, and preceded a Permo‐Triassic low‐P stage. The M2 event with garnet 2 postdates the corona formation around Permian monazite. Garnet 2 displays first increasing X_Ca at decreasing X_Mg, then increasing X_Ca and X_Mg, and finally decreasing X_Ca with increasing X_Mg, always at high Ca and Mg, and low Mn. This records a P–T evolution which passed through eclogite facies conditions and reached maximum temperatures at ~750 °C/14 kbar during decompression‐heating. A monazite 2 population (94–86 Ma) with lower Y and Gd contents crystallized at decreasing pressure during the Cretaceous (Eo‐Alpine) metamorphism M2 at a high‐P/T gradient. The Saualpe Eclogite Unit underwent two distinct clockwise metamorphic cycles at different P–T conditions, related to continental collisions under different thermal regimes. This led to a characteristic distribution pattern of monazite ages in this unit which is different from other Austroalpine basement areas.     

Dehydration of metapelites during high‐P metamorphism: The coupling between fluid sources and fluid sinks

Polymetamorphic metapelites and embedded eclogites share a complex, episodic interplay of dehydration and fluid infiltration at the eclogite type‐locality (Saualpe–Koralpe, Eastern Alps, Austria). The metapelites inherited a fluid content (i.e. mineral‐bound OH expressed in terms of mol.% H₂O) of ～6–7 mol.% H₂O from high‐T–low‐P metamorphism experienced during the Permian. At or near P_max of the subsequent Eoalpine event (～20 kbar and 680^°C), the breakdown of paragonite to Na‐rich clinopyroxene and kyanite in metapelites released a discrete pulse of hydrous fluid. Prior to the dehydration event, the rocks were largely fluid absent, allowing only limited re‐equilibration during the prograde Eoalpine evolution. Similarly, Permian‐aged gabbros have persisted metastably due to the absence of a catalyst prior to fluid‐induced re‐equilibration. The fluid triggered partial to complete eclogitization along a fluid infiltration front partially preserved in metagabbro. Near‐isothermal decompression to ～7.5–10 kbar and 670–690°C took place under fluid‐absent conditions. After decompression, a second breakdown of phengitic white mica and garnet produced muscovite, biotite, plagioclase and ～0.1–0.7 mol.% H₂O that enhanced extensive fluid‐aided re‐equilibration of the metapelites. Potential relicts of high‐P assemblages were largely obliterated and replaced by the recurrent amphibolite facies assemblage garnet+biotite+staurolite+kyanite+muscovite+plagioclase+ilmenite+quartz. The hydrous fluid originating from the metapelites infiltrated the embedded eclogites at these P–T conditions and induced the local breakdown of the peak assemblage omphacite and garnet to fine‐grained symplectites of diopside and plagioclase. Further fluid infiltration led to the formation of hornblende–quartz poikiloblasts at the expense of the symplectites. The metapelites re‐equilibrated until the growth of retrograde staurolite consumed any remaining free fluid, thereby terminating the process. Further re‐equilibration is inhibited by both the lack of a catalytic fluid and H₂O as a reactant essential for rehydration reactions. The interplay between fluid sources and fluid sinks describes a closed cycle for the rocks at the eclogite type‐locality. Final, near‐isobaric cooling is indicated by a slight increase of X_Fe in garnet rims. Post‐decompression dehydration and fluid‐aided re‐equilibration arrested by the introduction of staurolite might explain the apparently homogeneous retrogression conditions as well as the notorious absence of diagnostic high‐P assemblages in metapelites at the eclogite type‐locality.     

Evidence from mineral assemblages for infiltration of pelitic schists by aqueous fluids during metamorphism

Prograde mineral assemblages and compositions have been predicted for pelitic schist in the 10 component system Na₂O–K₂O–CaO–MnO–FeO–MgO–Al₂O₃–SiO₂–CO₂–H₂O for three cases of prograde metamorphism and fluid-rock interaction: (1) increasing temperature (T) at constant pressure (P) and constant pore fluid volume (1%) without infiltration (no-infiltration case); (2) increasing T at constant P accompanied by sufficient fluid infiltration that fluid composition is at all times constant (large-flux case); and (3) increasing T at constantP accompanied by a timeintegrated fluid flux f 10⁴ cm^{3 cm 2} (intermediate-flux case). Stable mineral assemblages and compositions were calculated by solving a system of non-linear equations that specify mass balance and chemical equilibrium between minerals and fluid. The model pelitic system includes quartz, muscovite, plagioclasc, chlorite, ankerite, siderite, biotite, garnet, staurolite, andalusite, kyanite, sillimanite, K-feldspar, and a coexisting, binary H₂O–CO₂ fluid. Specifically, prograde thermal metamorphism was modelled for Shaw's (1956) average low-grade pelite and for a moderate range of bulk rock compositions at P=3, 5, and 7 kb and initial fluids with Xco ₂ ^o =0.02–0.40. The model predicts a carbonate-bearing mineral assemblage for average pelite under chlorite zone conditions composed of quartz, muscovite, albite, chlorite, ankerite, and siderite. The mineral assemblages predicted for the noinfiltration case are unlike those typically observed in regional metamorphic terranes. Simulations of metamorphism for the large-flux and intermediate-flux cases, however, reproduce the sequence of mineral assemblages observed in normal Barrovian regional metamorphic terranes. These results suggest that regional metamorphism of pelitic schists is typically associated with infiltration of significant quantities of aqueous fluid.     

Pressure, temperature and fluid composition during amphibolite facies metamorphism of graphitic metapelites, Howard Ridge, British Columbia

ABSTRACT Graphitic metapelites from the Howard Ridge area, British Columbia, have been studied to estimate the pressure, temperature and fluid composition attending amphibolite facies metamorphism. Results from thermobarometric calculations indicate that P-T conditions of 610–625°C and 6.7kbar were reached during metamorphism. The equilibrium paragonite-quartz-albite-kyanite-H₂O gives significantly different estimates of XH₂O in the metamorphic fluid using different paragonite solution models. Estimates of XH₂O range from a maximum of 0.93 (Eugster et al., 1972) to a minimum of 0.29 (Chatterjee & Flux, 1986). H₂O estimates obtained using the Eugster et al. (1972) and Chatterjee & Froese (1975) solution models give similar results (i.e. 0.8 ± 0.1 versus 0.7 ± 0.1, respectively). Non-ideal mixing in the C-O-H system provides an XH₂O estimate of 0.74 at H₂O maximum conditions, 0.5 log units below the QFM buffer. The Chatterjee & Flux (1986) paragonite solution model provides unrealistically low estimates of XH₂O relative to other paragonite solution models, C-O-H equilibria, and published fluid inclusion and mineral equilibria data. Consistent estimates of fluid composition between C-O-H and mineral equilibria suggest that a H₂O-rich fluid attended metamorphism of graphitic metapelites at Howard Ridge.     

Refining the P–T records of UHT crustal metamorphism

Ultra‐high‐temperature (UHT) metamorphism occurs when the continental crust is subjected to temperatures of greater than 900 °C at depths of 20–40 km. UHT metamorphism provides evidence that major tectonic processes may operate under thermal conditions more extreme than those generally produced in numerical models of orogenesis. Evidence for UHT metamorphism is recorded in mineral assemblages formed in magnesian pelites, supported by high‐temperature indicators including mesoperthitic feldspar, aluminous orthopyroxene and high Zr contents in rutile. Recent theoretical, experimental and thermodynamic data set constraints on metamorphic phase equilibria in FMAS, KFMASH and more complex chemical systems have greatly improved quantification of the P–T conditions and paths of UHT metamorphic belts. However, despite these advances key issues that remain to be addressed include improving experimental constraints on the thermodynamic properties of sapphirine, quantifying the effects of oxidation state on sapphirine, orthopyroxene and spinel stabilities and quantifying the effects of H₂O–CO₂ in cordierite on phase equilibria and reaction texture analysis. These areas of uncertainty mean that UHT mineral assemblages must still be examined using theoretical and semi‐quantitative approaches, such as P(–T)–μ sections, and conventional thermobarometry in concert with calculated phase equilibrium methods. In the cases of UHT terranes that preserve microtextural and mineral assemblage evidence for steep or ‘near‐isothermal’ decompression P–T paths, the presence of H₂O and CO₂ in cordierite is critical to estimates of the P–T path slopes, the pressures at which reaction textures have formed and the impact of fluid infiltration. Many UHT terranes have evolved from peak P–T conditions of 8–11 kbar and 900–1030 °C to lower pressure conditions of 8 to 6 kbar whilst still at temperature in the range of 950 to 800 °C. These decompressional P–T paths, with characteristic dP/dT gradients of ～25 ± 10 bar °C^?1, are similar in broad shape to those generated in deep‐crustal channel flow models for the later stages of orogenic collapse, but lie at significantly higher temperatures for any specified pressure. This thermal gap presents a key challenge in the tectonic modelling of UHT metamorphism, with implications for the evolution of the crust, sub‐crustal lithosphere and asthenospheric mantle during the development of hot orogens.     

Subduction metamorphism of serpentinite‐hosted carbonates beyond antigorite‐serpentinite dehydration (Nevado‐Filábride Complex,Spain)

At sub‐arc depths, the release of carbon from subducting slab lithologies is mostly controlled by fluid released by devolatilization reactions such as dehydration of antigorite (Atg‐) serpentinite to prograde peridotite. Here we investigate carbonate–silicate rocks hosted in Atg‐serpentinite and prograde chlorite (Chl‐) harzburgite in the Milagrosa and Almirez ultramafic massifs of the palaeo‐subducted Nevado‐Filábride Complex (NFC, Betic Cordillera, S. Spain). These massifs provide a unique opportunity to study the stability of carbonate during subduction metamorphism at P–T conditions before and after the dehydration of Atg‐serpentinite in a warm subduction setting. In the Milagrosa massif, carbonate–silicate rocks occur as lenses of Ti‐clinohumite–diopside–calcite marbles, diopside–dolomite marbles and antigorite–diopside–dolomite rocks hosted in clinopyroxene‐bearing Atg‐serpentinite. In Almirez, carbonate–silicate rocks are hosted in Chl‐harzburgite and show a high‐grade assemblage composed of olivine, Ti‐clinohumite, diopside, chlorite, dolomite, calcite, Cr‐bearing magnetite, pentlandite and rare aragonite inclusions. These NFC carbonate–silicate rocks have variable CaO and CO₂ contents at nearly constant Mg/Si ratio and high Ni and Cr contents, indicating that their protoliths were variable mixtures of serpentine and Ca‐carbonate (i.e., ophicarbonates). Thermodynamic modelling shows that the carbonate–silicate rocks attained peak metamorphic conditions similar to those of their host serpentinite (Milagrosa massif; 550–600°C and 1.0–1.4 GPa) and Chl‐harzburgite (Almirez massif; 1.7–1.9 GPa and 680°C). Microstructures, mineral chemistry and phase relations indicate that the hybrid carbonate–silicate bulk rock compositions formed before prograde metamorphism, likely during seawater hydrothermal alteration, and subsequently underwent subduction metamorphism. In the CaO–MgO–SiO₂ ternary, these processes resulted in a compositional variability of NFC serpentinite‐hosted carbonate–silicate rocks along the serpentine‐calcite mixing trend, similar to that observed in serpentinite‐hosted carbonate‐rocks in other palaeo‐subducted metamorphic terranes. Thermodynamic modelling using classical models of binary H₂O–CO₂ fluids shows that the compositional variability along this binary determines the temperature of the main devolatilization reactions, the fluid composition and the mineral assemblages of reaction products during prograde subduction metamorphism. Thermodynamic modelling considering electrolytic fluids reveals that H₂O and molecular CO₂ are the main fluid species and charged carbon‐bearing species occur only in minor amounts in equilibrium with carbonate–silicate rocks in warm subduction settings. Consequently, accounting for electrolytic fluids at these conditions slightly increases the solubility of carbon in the fluids compared with predictions by classical binary H₂O–CO₂ fluids, but does not affect the topology of phase relations in serpentinite‐hosted carbonate‐rocks. Phase relations, mineral composition and assemblages of Milagrosa and Almirez (meta)‐serpentinite‐hosted carbonate–silicate rocks are consistent with local equilibrium between an infiltrating fluid and the bulk rock composition and indicate a limited role of infiltration‐driven decarbonation. Our study shows natural evidence for the preservation of carbonates in serpentinite‐hosted carbonate–silicate rocks beyond the Atg‐serpentinite breakdown at sub‐arc depths, demonstrating that carbon can be recycled into the deep mantle.