Constraints on the application of carbon isotope thermometry in high- to ultrahigh-temperature metamorphic terranes

Nine marble horizons from the granulite facies terrane of southern India were examined in detail for stable carbon and oxygen isotopes in calcite and carbon isotopes in graphite. The marbles in Trivandrum Block show coupled lowering of δ¹³C and δ¹⁸O values in calcite and heterogeneous single crystal δ¹³C values (? 1 to ? 10‰) for graphite indicating varying carbon isotope fractionation between calcite and graphite, despite the granulite facies regional metamorphic conditions. The stable isotope patterns suggest alteration of δ¹³C and δ¹⁸O values in marbles by infiltration of low δ¹³C–δ¹⁸O‐bearing fluids, the extent of alteration being a direct function of the fluid‐rock ratio. The carbon isotope zonation preserved in graphite suggests that the graphite crystals precipitated/recrystallized in the presence of an externally derived CO₂‐rich fluid, and that the infiltration had occurred under high temperature and low f_O2 conditions during metamorphism. The onset of graphite precipitation resulted in a depletion of the carbon isotope values of the remaining fluid+calcite carbon reservoir, following a Rayleigh‐type distillation process within fluid‐rich pockets/pathways in marbles resulting in the observed zonation. The results suggest that calcite–graphite thermometry cannot be applied in marbles that are affected by external carbonic fluid infiltration. However, marble horizons in the Madurai Block, where the effect of fluid infiltration is not detected, record clear imprints of ultrahigh temperature metamorphism (800–1000 °C), with fractionations reaching <2‰. Zonation studies on graphite show a nominal rimward lowering δ¹³C on the order of 1 to 2‰. The zonation carries the imprint of fluid deficient/absent UHT metamorphism. Commonly, calculated core temperatures are > 1000 °C and would be consistent with UHT metamorphism.     

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.     

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.     

Garnet—biotite gneiss in ‘Système du Graphite’ (Madagascar): Petrology and fluid inclusions

Primary ‘carbonic’ fluid inclusions filled with nearly pure high density CO₂ occur in garnet in a garnet—biotite gneiss from ‘Système du Graphite’, Komajia, Madagascar (Malagasy). They have been formed during syntectonic growth of the garnet under granulite facies conditions. Most of the biotite appears to have crystallized later than the garnet under the influence of more water rich fluids.     

Granulite facies metasomatism: zoned calc-silicate boudins from the Rauer Group,East Antarctica

Calc-silicate boudins from the Rauer Group, East Antarctica, were metamorphosed under granulite facies conditions during late Proterozoic (ca. 1,000 Ma) M3 metamorphism. Boudin cores contain low to moderate a_{CO 2} assemblages including wollastonite, grossularandradite (grandite) garnet, clinopyroxene, scapolite, plagioclase, quartz±calcite. Petrological and stable isotopic evidence suggests that these core assemblages resulted from pre-peak M3 infiltration of water-rich fluids; there is no evidence for a pervasive fluid phase under peak M3 conditions. The boudins are separated from the surrounding Fe-rich pelites and semi-pelites by a series of concentric, high-variance reaction zones developed under peak M3 conditions. Variations in mineral assemblage, mineral composition and whole rock composition across these zones suggest that they formed by diffusional masstransfer, controlled principally by a chemical potential gradient in Ca across the original calc-silicate-paragneiss lithological boundary. As a consequence of the nearcomplete decarbonation of the calc-silicatesbefore the M3 peak, development of the diffusion-controlled reaction zones did not liberate significant CO₂ during granulite facies metamorphism. Similar calcite-poor, low a_{CO 2} calc-silicate horizons in other granulite facies terrains are unlikely to have been important local fluid sources during deep crustal metamorphism.     

Vein graphite deposits: geological settings,origin, and economic significance

Graphite deposits result from the metamorphism of sedimentary rocks rich in carbonaceous matter or from precipitation from carbon-bearing fluids (or melts). The latter process forms vein deposits which are structurally controlled and usually occur in granulites or igneous rocks. The origin of carbon, the mechanisms of transport, and the factors controlling graphite deposition are discussed in relation to their geological settings. Carbon in granulite-hosted graphite veins derives from sublithospheric sources or from decarbonation reactions of carbonate-bearing lithologies, and it is transported mainly in CO₂-rich fluids from which it can precipitate. Graphite precipitation can occur by cooling, water removal by retrograde hydration reactions, or reduction when the CO₂-rich fluid passes through relatively low-fO₂ rocks. In igneous settings, carbon is derived from assimilation of crustal materials rich in organic matter, which causes immiscibility and the formation of carbon-rich fluids or melts. Carbon in these igneous-hosted deposits is transported as CO₂ and/or CH₄ and eventually precipitates as graphite by cooling and/or by hydration reactions affecting the host rock. Independently of the geological setting, vein graphite is characterized by its high purity and crystallinity, which are required for applications in advanced technologies. In addition, recent discovery of highly crystalline graphite precipitation from carbon-bearing fluids at moderate temperatures in vein deposits might provide an alternative method for the manufacture of synthetic graphite suitable for these new applications.     

Geochemical constraints of the eclogite and granulite facies metamorphism as recognized in the Raobazhai complex from North Dabie Shan,China

A combined study of major and trace elements, fluid inclusions and oxygen isotopes has been carried out on garnet pyroxenite from the Raobazhai complex in the North Dabie Terrane (NDT). Well‐preserved compositional zoning with Na decreasing and Ca and Mg increasing from the core to rim of pyroxene in the garnet pyroxenite indicates eclogite facies metamorphism at the peak metamorphic stage and subsequent granulite facies metamorphism during uplift. A P–T path with substantial heating (from c. 750 to 900 °C) after the maximum pressure reveals a different uplift history compared with most other eclogites in the South Dabie Terrane (SDT). Fluid inclusion data can be correlated with the metamorphic grade: the fluid regime during the peak metamorphism (eclogite facies) was dominated by N₂‐bearing NaCl‐rich solutions, whereas it changed into CO₂‐dominated fluids during the granulite facies retrograde metamorphism. At a late retrograde metamorphic stage, probably after amphibolite facies metamorphism, some external low‐salinity fluids were involved. In situ UV‐laser oxygen isotope analysis was undertaken on a 7 mm garnet, and impure pyroxene, amphibole and plagioclase. The nearly homogeneous oxygen isotopic composition (δ¹⁸O_VSMOW = c. 6.7‰) in the garnet porphyroblast indicates closed fluid system conditions during garnet growth. However, isotopic fractionations between retrograde phases (amphibole and plagioclase) and garnet show an oxygen isotopic disequilibrium, indicating retrograde fluid–rock interactions. Unusual MORB‐like rare earth element (REE) patterns for whole rock of the garnet pyroxenite contrast with most ultra‐high‐pressure (UHP) eclogites in the Dabie‐Sulu area. However, the age‐corrected initial ε_Nd(t) is ? 2.9, which indicates that the protolith of the garnet pyroxenite was derived from an enriched mantle rather than from a MORB source. Combined with the present data of oxygen isotopic compositions and the characteristic N₂ content in the fluid inclusions, we suggest that the protolith of the garnet pyroxenite from Raobazhai formed in an enriched mantle fragment, which has been exposed to the surface prior to the Triassic metamorphism.     

变质流体研究新进展

变质流体是变质过程的主要动力学因素之一。目前变质流体研究主要集中在下部地壳麻粒岩相变质流体，俯冲带高压－超高压变质流体和接触变质流体等方面。研究的主要问题是流体流动机制和元素迁移，流体－岩石相互作用和流体来源。下部地壳麻粒岩相变质流体以ＣＯ２为主，具有较低的ａＨ２Ｏ。δ１３Ｃ研究表明大约２／３ＣＯ２是深成的。富ＣＯ２流体流动是紫苏花岗岩形成和热扰动的原因之一，也是麻粒岩形成和大离子亲石元素亏损的主要因素。俯冲带是高压、超高压变质作用发生和流体活动最活跃的场所。流体富含Ｈ２Ｏ、ＣＨ４和ＣＯ２，可以诱导部分熔融反应和岛弧岩浆作用。高压变质条件下的矿物稳定性也与流体有关。同位素研究表明，在超高压变质期间没有化学上完全相同的流体大规模循环。流体－熔体系统模式能更有效地解释下插板片的元素再循环。接触变质流体研究主要集中在含有易于发生流体－岩石反应的不纯碳酸盐岩地区。硅灰石带中流体／岩石比率高达４０∶１，表明接触变质岩石中有大量流体存在。接触变质过程流体成分有较大差异，主要取决于流体来源、原岩性质和侵入体特征。流体流动和循环模式受控于构造变形，岩浆作用和变质过程的动力学条件及流体成分。     

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.     

Evolution of metamorphic fluid recorded in granulite facies metacarbonate rocks from the middle segment of the Mogok metamorphic belt in central Myanmar

The Mogok metamorphic belt of Palaeogene age, which records subduction‐ and collision‐related events between the Indian and Eurasian plates, lies along the western margin of the Shan plateau in central Myanmar and continues northwards to the eastern Himalayan syntaxis. Reaction textures of clinohumite‐ and scapolite‐bearing assemblages in Mogok granulite facies metacarbonate rocks provide insights into the drastic change in fluid composition during exhumation of the collision zone. Characteristic high‐grade assemblages of marble and calcsilicate rock are clinohumite+forsterite+spinel+phlogopite+pargasite/edenite+calcite+dolomite, and scapolite+diopside+anorthite+quartz+calcite respectively. Calculated petrogenetic grids in CaO–MgO–Al₂O₃–SiO₂–H₂O–CO₂ and subsets of this system were employed to deduce the pressure–temperature–fluid evolution of the clinohumite‐ and scapolite‐bearing assemblages. These assemblages suggest higher temperature (>780–810°C) and [=CO₂/(CO₂+H₂O) >0.17–0.60] values in the metamorphic fluid for the peak granulite facies stage, assuming a pressure of 0.8 GPa. Calcite grains commonly show exsolution textures with dolomite particles, and their reintegrated compositions yield temperatures of 720–880°C. Retrograde reactions are mainly characterized by a reaction zone consisting of a dolomite layer and a symplectitic aggregate of tremolite and dolomite grown between clinohumite and calcite in marble, and a replacement texture of scapolite by clinozoisite in calcsilicate rock. These textures indicate that the retrograde reactions developed under lower temperature (<620°C) and (<0.08–0.16) conditions, assuming a pressure of 0.5 GPa. The metacarbonate rocks share metamorphic temperatures similar to the Mogok paragneiss at the peak granulite facies stage. The values of the metacarbonate rock at peak metamorphic stage are, however, distinctly higher than those previously deduced from carbonate mineral‐free paragneiss. Primary clinohumite, phlogopite and pargasite/edenite in marble have F‐rich compositions, and scapolite in calcsilicate rock contains Cl, suggesting a contrast in the halogen compositions of the metamorphic fluids between these two lithologies. The metamorphic fluid compositions were probably buffered within each lithology, and the effective migration of metamorphic fluid, which would have extensively changed the fluid compositions, did not occur during the prograde granulite facies stage throughout the Mogok metamorphic belt. The lower conditions of the Mogok metacarbonate rocks during the retrograde stage distinctly contrast with higher conditions recorded in metacarbonate rocks from other metamorphic belts of granulite facies. The characteristic low conditions were probably due to far‐ranging infiltration of H₂O‐dominant fluid throughout the middle segment of the Mogok metamorphic belt under low‐amphibolite facies conditions during the exhumation and hydration stage.     

Carbon isotope thermometry in marbles of the Adirondack Mountains, New York

Abstract Carbon isotope thermometry has been applied to coexisting calcite and graphite in marbles from throughout the Adirondack Mountains, New York. Eighty-nine calcite-graphite pairs from the amphibolite grade NW Adirondacks change systematically in temperature north-westwards from 680 to 640 to 670° C over a 30-km distance, reflecting transitions from amphibolite facies towards granulite facies to the north-west and to the south-east. Temperature contours based on calcite-graphite thermometry in the NW Adirondacks parallel mineral isograds, with the orthopyroxene isograd falling above 675° C, and indicate that regional metamorphic temperatures were up to 75° C higher than temperatures inferred from isotherms based on cation and solvus thermometry (Bohlen et al. 1985). Fifty-five calcite-graphite pairs from granulite grade marbles of the Central Adirondacks give regional metamorphic temperatures of 670–780° C, in general agreement with cation and solvus thermometry. Data for amphibolite and granulite grade marbles show a 12%oo range in δ¹³C_cal and δ¹³C_gr. A strong correlation between carbon isotopic composition and the abundance of graphite (C_gr/C_rock) indicates that the large spread in isotopic compositions results largely from exchange between calcite and graphite during closed system metamorphism. The trends seen in δ¹³C _vs. C_gr/C_rock and δ¹³C_cal vs. δ¹³C_gr could not have been preserved if significant amounts of CO₂-rich fluid had pervasively infiltrated the Adirondacks at any time. The close fit between natural data and calculated trends of δ¹³C vs. C_gr/C_rock indicates a biogenic origin for Adirondack graphites, even though low δ¹³C values are not preserved in marble. Delamination of 17 graphite flakes perpendicular to the c-axis reveals isotopic zonation, with higher δ¹³C cores. These isotopic gradients are consistent with new graphite growth or recrystallization during a period of decreasing temperature, and could not have been produced by exchange with calcite on cooling due to the sluggish rate of diffusion in graphite. Samples located >2km from anorthosite show a decrease of 0.5-0.8%oo in the outer 100 μ of the grains, while samples at distances over 8 km show smaller core-to-rim decreases of c.0.2%oo. Correlation between the degree of zonation and distance to anorthosite suggests that the isotopic profiles reflect partial overprinting of higher temperature contact metamorphism by later granulite facies metamorphism. Core graphite compositions indicate contact metamorphic temperatures were 860–890° C within 1 km of the Marcy anorthosite massif. If samples with a significant contact metamorphic effect (Δ(_cal-gr) <3.2%oo) are not included, then the remaining 38 granulite facies samples define the relation Δ¹³C(_cal-gr) = 3.56 ± 10⁶T^-2 (K).     

Derivation of gold by oxidative metamorphism of a deep ductile shear zone: Part 1. Conceptual model

Quartz-carbonate gold deposits were emplaced in shear zones at or above the brittle-ductile transition. Some of the largest deposits are known to have formed along major, long-lived, transcurrent shears. Shears of this type widened downwards in the ductile regime, as a result of decreasing rock viscosity with depth; some were as wide as 40 km at depths of granulite facies metamorphism. Ductile shears are permeable and, since the permeability is along microfractures, fluid flow was pervasive, providing the opportunity for extensive chemical reaction. Reaction rates were enhanced by shear heating and by deformation-induced stress gradients in minerals, and reductions in grain size. Fluid flow tended to be upwards, because of pressure drop into the brittle portion of the shear. Given the wedge-shaped profile of ductile shears, fluids that had passed through a large volume of lower crust would have been focused at the brittle-ductile transition. Thus, if processes existed to selectively remove elements during fluid movement through the lower crust, these elements would also have been focused at this transition.One of the most constant features of quartz-carbonate lodes is carbonate alteration, which may extend kilometers out from major deposits. The ¹³C signature of this is consistent with a mantle source for the CO₂. Upward-moving CO₂ vapour of probable mantle origin has been implicated in the dehydration of amphibolite facies rocks to granulites and the concomitant depletion of large ion lithophile elements (LILE). The best documented cases of modification of the lower crust by CO₂ are from major shear zones. CO₂ streaming at depth could only have occurred under conditions more oxidizing than that required for graphite stability. These conditions favour solubility of gold by (a) oxidizing Au⁰ to Au⁺; (b) by dissolving sulphide from the rocks to complex with Au⁺. Recent work has shown that some major Archean gold deposits were derived from relatively oxidized fluids.A conceptual model is outlined for the genesis of at least some quartz-carbonate gold deposits. CO₂ permeating deep ductile shear zones dehydrated amphibolite facies rocks. A relatively oxidized CO₂-H₂O fluid was produced, which dissolved sulphide and gold from large volumes of lower crust. Gold was carried upwards in the narrowing shear, to be focused and precipitated at or above the brittle-ductile transition.     

Fluid inclusion studies on the Koraput Alkaline Complex,Eastern Ghats Province,India: Implications for mid-Neoproterozoic granulite facies metamorphism and exhumation

Following ultrahigh temperature granulite metamorphism at ∼1 Ga, the Eastern Ghats Province of India was intruded by the Koraput Alkaline Complex, and was subsequently re-metamorphosed in the granulite facies in the mid-Neoproterozoic time. Fluid inclusion studies were conducted on silica undersaturated alkali gabbro and syenites in the complex, and a pre-metamorphic pegmatitic granite dyke that intrudes it. High density (1.02–1.05 g/cc), pseudo-secondary pure CO₂ inclusions are restricted to metamorphic garnets within the gabbro and quartz within the granite, whereas moderate (∼0.92–0.95 g/cc) and low density (∼0.75 g/cc) secondary inclusions occur in garnet, magmatic clinopyroxene, plagioclase, hornblende and quartz. The isochores calculated for high density pseudo-secondary inclusions pass very close to the peak metamorphic window (∼8 kbar, 750 °C), and are interpreted to represent the fluid present during peak metamorphism that was entrapped by the growing garnet. Microscopic round inclusions of undigested, relict calcite in garnet suggest that the CO₂ present during metamorphism of the complex was internally derived through carbonate breakdown. Pure to low salinity (0.00–10.1 wt% NaCl equivalent) aqueous intra-/intergranular inclusions showing unimodal normal distribution of final ice-melting temperature (T_m) and temperature of homogenization (T_h) are present only in quartz within the granite. These represent re-equilibrated inclusions within the quartz host that were entrapped at the metamorphic peak. Rare, chemically precipitated graphite along the walls of carbonic inclusions is interpreted as a post-entrapment reaction product formed during decompression. The fluid inclusion evidence is consistent with rapid exhumation of a thickened lower crust following the mid-Neoproterozoic granulite facies metamorphic event. The study suggests that mantle CO₂, transported by alkaline magma into the crust, was locked up within carbonates and released during granulite metamorphism.     

Rare-earth element geochemistry of Madras granulites

Archaean granulites from the type charnockite locality of Pallavaram, Madras City, Tamil Nadu, southern India consist of a bimodal suite of basic and silicic orthogneisses, associated with metasedimentary gneisses (khondalites). Charnockite is the dominant rock type. Basic granulites display a tholeiitic trend of strong iron enrichment accompanied by an increase in the concentration of the rare earth elements (REE), and the development of appreciable negative europium anomalies. These trends are considered to reflect low pressure fractional crystallisation of pyroxene-plagioclase assemblages under conditions of lowf _{O 2}. Ultramafic granulites may represent the cumulus material of such a process. The silicic granulites (charnockites) are generally K₂O rich and in marked contrast to the low K₂O (tonalitic) silicic gneisses which dominate most granulite facies terrains. Their REE abundances, however, embrace the complete range of patterns observed in both K-rich and K-poor Archaean gneisses. The presence of a large number of pre-granulite facies potassic pegmatites in the area suggests metasomatism of an originally less potassic suite of rocks. Trace element considerations lead to a model whereby metasomatism and partial fusion of silicic gneisses in the terrain preceded the granulite facies metamorphic event. This sequence of events is best related to fluctuations in the composition of metamorphic fluids in the lower crust.     

Millimetre-scale variation in metamorphic permeability of marbles during transient fluid flow: an example from the Reynolds Range, central Australia

Fluid inclusions from a biotite-garnet schist in the Southern Aravalli Mountain Belt (India) give information on both peak metamorphic conditions and post-peak metamorphic processes during uplift. A combination of careful petrography, microthermometry and Raman spectroscopy reveals the presence of at least five generations of enclosed fluids. Lower amphibolite-facies pressure-temperature conditions of the growth of garnet rims are reproduced by the highest fluid density of the relatively oldest inclusion type of CO₂ (±N₂)-rich compositions. A calculated fluid composition in the COH system, in equilibrium with the graphite buffer corresponds to a CO₂-rich fluid at metamorphic conditions. However, the results of these calculations are very sensitive to small fluctuations in oxygen fugacity and the accuracy of thermodynamic properties of mineral equilibria. Re-equilibration, conceived by specific size-density distribution and the absence of an aqueous phase in inclusions that contain nahcolite crystals, is monitored in these inclusions as post-peak metamorphic processes, like partial decrepitation and preferential leakage. The other fluid types represent heterogeneous fluid trapping of coexisting aqueous NaCl-bearing solutions with CO₂-CH₄-rich vapour bubbles in healed cracks, and probably the introduction of external fluids containing high salinity aqueous CaCl₂-rich solutions in nearly pure N₂ vapour bubbles, at lower P-T conditions. This study illustrates that fluid inclusions remain a valuable database of peak metamorphic conditions, moreover, alterations of the entrapped fluids and surrounding crystals are illustrative for specific exhumation evolutions. Received: 24 March 1999 / Accepted: 13 January 2000     

Granulites,CO2 and graphite

Externally derived, pure CO₂ that mixes with a carbon-(under)saturated C-O-H fluid in lower crustal granulites may result in graphite precipitation if the host-rock oxygen fugacity (f_O2^rock) is below the upper f_O2 limit of graphite. The maximum relative amount of graphite that can precipitate varies between a few mol% up to more than 25 mol%, depending on pressure, temperature, and host-rock redox state. The maximum relative amount of graphite that can precipitate from an infiltrating CO₂ fluid into a dry granulite (CO fluid system) varies between zero and a few mol%. Thermodynamic evaluation of the graphite precipitation process shows that CO₂ infiltration into lower crustal rocks does not always result in a carbon (super)saturated fluid. In that case, graphite precipitation is only possible if carbon saturation can be reached as a result of the reaction CO₂ → CO + ½ O₂. Graphite that has been precipitated during granulite facies metamorphic conditions can subsequently be absorbed by a COH fluid during retrograde metamorphism. It is also possible, however, that significant amounts of graphite precipitate from a COH fluid during retrograde metamorphism. This study shows that interpreting the presence or absence of graphite in granulites with respect to CO₂ infiltration requires detailed information on the P–T–f_O2^rock conditions, the relative amount of CO₂ that infiltrates into the rock, and whether H₂O is present or not.     

Phase equilibria for graphitic metapelite including solution of CO2 in melt and cordierite: implications for dehydration,partial melting and graphite precipitation

When graphite is present, carbon‐bearing species dissolve in the C‐O‐H fluid and lower the activity of water (). Accordingly, metamorphic reactions that involve water, namely dehydration and partial melting reactions, adjust their P–T positions to accommodate the change of . In this modelling study, pseudosections are calculated for graphite‐bearing systems that are either closed or that progressively lose fluid and/or melt. The diagrams incorporate a new model of CO₂ solubility in felsic melts that we derived to be compatible with a recently published melt model. As the result of the lowered in the carbon‐bearing systems, the temperature displacements of the solidus can be as large as 50 °C at low pressures in cordierite‐bearing zones (<4 kbar), but are smaller than 15 °C at mid‐pressure P–T conditions (4–9 kbar). In the supersolidus region, the phase relations among silicate minerals + melt are very close to those in carbon‐free systems. The fluid CO₂ content increases as temperature increases in the supersolidus assemblages. The CO₂‐rich fluid can be stable in granulite facies conditions in an oxidized system. In graphitic systems, melt and/or cordierite dominate the CO₂ budget of high‐grade rocks. During cooling, the fluid that exsolves from such crystalizing melt is CO₂‐rich. In addition to the phase relations, the pseudosections presented in this study enable researchers to quantitatively investigate the evolution of phase modes, including graphite, along specific metamorphic P–T paths. At low pressures in the cordierite stability field, graphite is predicted to precipitate as the pressure increases or temperature decreases in the subsolidus assemblages, or temperature increases in the region of melt + fluid coexistence. On the other hand, the graphite abundance remains nearly constant along the mid‐pressure P–T series, but the graphite mode in the supersolidus region may increase due to residual enrichment if the melt is extracted. The modelling results show that metamorphic processes in closed systems lead to only small changes in graphite mode (a few tenths of a per cent). This strongly suggests that open‐system behaviours are required for large amounts of graphite deposition, including fluid infiltration and mixing or residual enrichment processes in high‐grade rocks. In addition to P–T pseudosections, P/T–X_O diagrams (X_O = O/(H + O) in the fluid) illustrate the thermodynamic features of internal buffering from another perspective, and explore the dependence of phase relations on the externally imposed redox state. If the system is equilibrated with CO₂ or CH₄‐rich infiltrating fluid, the temperature displacements of metamorphic reactions can be larger than 50 °C, compared with carbon‐free systems.     

Fluid inclusions in high-pressure granulites of the Pan-African belt in Tanzania (Uluguru Mts): a record of prograde to retrograde fluid evolution

The high-pressure granulites of the Uluguru Mountains are part of the Pan-African belt of Tanzania, the metamorphic evolution of which is characterized by an anticlockwise P-T path. Mineral assemblages that represent distinct metamorphic stages are selected for fluid inclusion studies in order to deduce the fluid evolution in metapelites and pyroxene granulites from the prograde to the retrograde stage. Fluid inclusion data improve the petrologically derived P-T path and confirm the anticlockwise evolution. Fluid inclusions in quartz enclosed in garnet porphyroblasts in metapelites preserve prograde fluids of CO₂–N₂ composition and later-trapped pure CO₂. During isochoric heating at temperatures near the peak of metamorphism, deformation and recrystallization led to fluid homogenization yielding N₂-poor CO₂ composition in the metapelites. Near-peak CO₂–N₂ fluid inclusions in quartz of metapelites and CO₂ inclusions in garnet-pyroxene granulites are characterized by perfect negative crystal shape. Garnet formed in veins and as coronas around orthopyroxene represent the near-isochoric/isobaric cooling stage which is characterized by high-density CO₂-rich fluid inclusions. Up to 15 mol% N₂ in some primary CO₂ inclusions in corona garnet indicate small-scale fluid heterogeneity during the static garnet growth. The fact that high-density fluid inclusions are preserved, suggests a shallow dP/dT slope of the uplift path. Nevertheless, some fluid inclusions decrepitated or re-equilibrated and low-density CO₂ inclusions were trapped in the garnet-pyroxene granulite while N₂–CH₄ inclusions formed in the metapelites. Different fluid compositions in metapelite and metabasite argue for an internal control of the fluid composition by phase equilibria. In shear zones where the pyroxene granulite was transformed into scapolite-biotite schist, CO₂–N₂ and low-density N₂–CH₄ fluid inclusions indicate several stages of tectonic activity and suggest fluid influx from the nearby metapelites. High- and low-salinity aqueous inclusions observed beside CO₂ inclusions in garnet-pyroxene granulites, in vein quartz and shear zones could be of high-grade origin but are mainly re-equilibrated or re-trapped along healed microfractures during lower-grade stages. Received: 21 May 1997 / Accepted: 6 October 1997     

P—T—t—deformation—fluid characteristics of lode gold deposits: evidence from alteration systematics

Structurally hosted lode gold-bearing quartz vein systems in metamorphic terranes possess many characteristics in common, spatially and through time; they constitute a single class of epigenetic precious metal deposit, formed during accretionary tectonics or delamination. The ore and alteration paragenesis encode numerous intensive and extensive variables that constrain the pressure—temperature—time—deformation—fluid (P—T—t—d—f) evolution of the host terrane and hence the origin of the deposits. The majority of lode gold deposits formed proximal to regional translithospheric terrane—boundary structures that acted as vertically extensive hydrothermal plumbing systems; the structures record variably thrust, and transpressional—transtensional displacements. Major mining camps are sited near deflections, strike slip or thrust duplexes, or dilational jogs on the major structures. In detail most deposits are sited in second or third order splays, or fault intersections, that define domains of low mean stress and correspondingly high fluid fluxes. Accordingly, the mineralization and associated alteration is most intense in these flanking domains. The largest lode gold mining camps are in terranes at greenschist facies; they possess greenschist facies hydrothermal alteration assemblages developed in cyclic ductile to brittle deformation that reflects interseismic—coseismic cycles. Interseismic episodes involve the development of ductile S—C shear zone fabrics that lead to strain softening. Pressure solution and dislocation glide microstructures signify low differential stress, slow strain rates of ≤ 10⁻¹³ s⁻¹, relatively high confining stress, and suprahydrostatic fluid pressures. Seismic episodes are induced by buildup of fluid pressures to supralithostatic levels that induce hydraulic fracturing with enhanced hydraulic conductivity, accompanied by massive fluid flow that in turn generates mineralized quartz veins. Hydrothermal cementing of ductile fabrics creates ‘hardening’, lowers hydraulic conductivity, and hence promotes fault valve behaviour. Repeated interseismic (fault valve closed), coseismic (valve open) cycles results in banded and/or progressively deformed veins. Alteration during both interseismic and coseismic episodes typically involves the hydrolysis of metamorphic feldspars and Fe, Mg, Ca-silicates to a muscovite/paragonite—chlorite ± albite/K-feldspars assemblage; carbonization of the metamorphic minerals to Ca, Fe, Mg-carbonates; and sulphidation of Fe-silicates and oxides to sulphides. Geochemically this is expressed as additions of K, Rb, Ba, Cs, and the volatiles H₂O, CO₂, CH₄, H₂S in envelopes of meter to kilometer scale. K/Rb and K/Ba ratios are close to average crustal values, potentially ruling out late stage magmatic fluids where K/Rb and K/Ba are respectively lower and higher than crustal values. Smaller deposits are present in subgreenschist, and amphibolite to granulite facies terranes. The former are characterized by subgreenschist facies alteration assemblages, vein stockworks, brittle fracturing and cataclastic microstructures, whereas the latter feature amphibolite to granulite facies alteration assemblages, ductile shear zones, ductilely deformed veins, and microstructures indicative of dislocation climb during interseismic episodes. Hence the lode gold deposits constitute a crustal continuum of deposits from subgreenschist to granulite facies, that all formed synkinematically in broad thermal and rheological equilibrium with their host terranes. These characteristics, combined with the low variance of alteration assemblages in the higher temperature deposits, rules out those being metamorphosed counterparts of greenschist facies deposits. Deposits at all grades have a comparable metal inventory with high concentrations of Au and Ag, where Au/Ag averages 5, with enrichments of a suite of rare metals and semi-metals (As, Sb, ± Se, Te, Bi, W, Mo and B), but low enrichments of the base (Cu, Pb, Zn, Cd) and other transition (Cr, Ni, Co, V, PGE, Sc) metals relative to average crust. The hydrothermal ore-forming fluids were dilute, aqueous, carbonic fluids, with salinities generally ≤ 3 wt.% NaCl equivalent, and X_{(CO2 ± CH4)} 10–24 wt.%. They possess low Cl but relatively high S, possibly reflecting the fact that metamorphic fluids are generated in crust with ∼ 200 ppm Cl, but ∼ 1 wt.%S. Primary fluid inclusions are: (1) H₂OCO₂, (2) CO₂-rich with variable CH₄ and small amounts of H₂O, and (3) 2-phase H₂O (liquid-vapor) inclusions. Inclusion types 2 and 3 represent immiscibility of the type 1 original ore fluid. Immiscibility was triggered by fluid pressure drop during the coseismic events and possibly by shock nucleation, leading to highly variably homogenization temperatures in an isothermal system. A thermodynamic evaluation of alteration assemblages constrains the ore fluid pH to 5–6; redox controlled by the HSO₄/H₂S and CO₂/CH₄ buffers; and X_CO2 that varies. The higher temperature deposits formed under marginally more oxidizing conditions. Stable isotope systematics of the ore and gangue minerals yields temperatures of 200–420°C, consistent with the crustal spectrum of the deposits, very high fluid rock ratios, and disequilibrium of the externally derived ore fluids with wall rocks. The ore fluid δD and δ¹⁸O overlap the metamorphic and magmatic ranges, but the total dataset for all deposits is consistent only with dominantly metamorphic fluids. Carbon isotope compositions of carbonates span −11 to +2% and show provinciality: this is consistent with variable proportions of reduced C (low δ¹³C) and oxidized C (higher δ¹³C) in the source regions contributing CO₂ and CH₄ to the ore fluids. In some instances, C appears to have been derived dominantly from proximal to the deposits, as in the Meguma terrane (δ¹³C ∼ − 22%). Sulphur isotope compositions range from 0 to +9‰, and are consistent with magmatic S, dissolution or desulphidation of magmatic sulphides, or average crustal sulphides. ³⁴S-depleted sulphides occur in ore bodies such as Hemlo where fluid immiscibility led to loss of H₂S and consequent fluid oxidation. Gold is probably transported as an Au(HS)⁻₂ complex. Relatively high S but low Cl in the hydrothermal fluid may explain the high Au slow base metal characteristic of the deposits. Gold precipitated in ore bodies due to loss of S from the ore fluid by sulphidation of wall rock, or immiscibility of H₂S; and by oxidation or reduction of the fluid, or by chemisorption, or some combination of these processes. Most lode gold deposits have been brittly reactivated during uplift of host terranes, with secondary brines or meteoric water advecting through the structures. These secondary fluids may remobilize gold, generate retrograde stable isotope shifts, reset mineral geochronometers, and leave trails of secondary fluid inclusions. Data on disturbed minerals has led to invalid models for lode gold deposits. The sum of alteration data leads to a model for lode gold deposits involving a clockwise P—T—t evolution and synkinematic and synmetamorphic mineralization of the ‘deep later’ type. During terrane accretion oceanic crust and sediments are subcreted beneath the terrane boundary. Thermal equilibration generates metamorphic fluids that advect up the terrane structure, at lithostatic fluid pressure, into the seismogenic zone where the majority of deposits form. Thus many lode gold deposits are on intrinsic part of the development of subduction—accretion complexes of the high-T, low-P type.     

Uranium and boron distributions related to metamorphic microstructure-evidence for metamorphic fluid activity

The distribution of uranium and boron in polymetamorphosed, granulite facies schists and gneisses has been studied using particle track methods. The concentration and distribution of these elements when examined in relation to mineralogy and microstructure provide an insight into: (1) the behaviour of U and B in metamorphism, (2) the activity of a fluid phase in the metamorphic processes and (3) the nature of chemical processes during schistosity development. A low concentration of primary U occurs in micro-inclusions of apatite and zircon (many are metamict) in the granulite facies M₁ assemblage. This assemblage which lacks B, except for zoned sillimanite, has undergone a localized retrograde metamorphism RM₁ characterised by hydrous alteration products containing abundant U and B. The RM₁ metamorphism is attributed to fluids generated during granulite facies dehydration reactions. A schistosity S₂ defined by M₂ fibrolite aggregates overprints the M₁ events. It is associated with (1) intragranular U concentrated in M₂ apatite and titanium bearing minerals and (2) abundant intergranular U within the fibrolite aggregates. High B contents also occur with the fibrolite. The S₂ schistosity appears to develop in a metamorphic environment containing a fluid enriched in U and B.