Fluid inclusion studies of gold-bearing quartz veins from the Yirisen deposit,Sula Mountains greenstone belt,Masumbiri, Sierra Leone

The auriferous veins at Yirisen, Masumbiri, Sierra Leone, occurring mainly in the form of sericitic quartz-sulphide lodes and stringers, are hosted in metamorphosed volcano-sedimentary assemblages invaded by at least two generations of granitic intrusions. Detailed microthermometric studies of fluid inclusions from the veins coupled with laser Raman spectroscopic analysis show that the inclusions contain aqueous fluids of variable salinity (5 to 60 wt.% NaCl equivalent) and dense carbonic fluids (pure CO₂: 1.08>d>0.88 g/cm³). Optical observations and analysis on opened inclusions by scanning electron microscopy (SEM) reveal that some of the aqueous inclusions contain a number of daughter minerals: halite, sylvite, Ca-, Fe-, Mg- and possibly Li-bearing chlorides, and anhydrite; nahcolite occurs also in some of the CO₂ inclusions. The SEM runs also detected a small amount of electrum, suggesting that silver might be a bi-product of the mineralisation. The aqueous and carbonic fluids remained immiscible throughout the formation and evolution of the hydrothermal veins. A few mixed (H₂O+CO₂) inclusions apparently resulted from accidental trapping of both fluids in the same cavity. The wide range of salinities observed in the aqueous inclusions is attributed to the mixing of relatively hot, low-salinity aqueous fluids and colder, high-salinity brines. The CO₂-rich and low-salinity H₂O inclusions are considered to be derived from the metamorphic decarbonation/dehydration of the greenstone pile whilst the high-salinity brines are believed to be basinal in origin. Pressure–temperature (P–T) conditions of entrapment, inferred from the intersection of representative isochores of the immiscible fluids, indicate that the formation of the veins started at T=400°C and P about 4 kbar, in the presence of the high-density CO₂ and low-salinity H₂O fluids. At about 200°C, pressure fluctuations (incremental opening of the vein) correspond to the trapping of the lower-density CO₂ inclusions and high-salinity brines. It is proposed that the decarbonation/dehydration processes (possibly aided by later magmatic processes) expelled and mobilised the gold from the greenstone pile and concentrated it in the CO₂-bearing hydrothermal fluid in the form of Au–chloride complexes. High thermal gradients are believed to have caused the upward migration of this fluid from the bottom of the greenstone pile through structurally controlled conduits. We contend that phase separation of the H₂O–CO₂ metamorphic fluid, aided possibly by some wall–rock alteration, most probably triggered a decrease in ligand activity and thus, precipitation of the gold into lodes. Percolation of the basinal brines is thought to have remobilised some of the gold together with some silver.     

Evidence of magmatic CO2-rich fluids in peraluminous graphite-bearing leucogranites from Deep Freeze Range (northern Victoria Land,Antarctica)

Fine-grained peraluminous synkinematic leuco-monzogranites (SKG), of Cambro-Ordovician age, occur as veins and sills (up to 20–30 m thick) in the Deep Freeze Range, within the medium to high-grade metamorphics of the Wilson Terrane. Secondary fibrolite + graphite intergrowths occur in feldspars and subordinately in quartz. Four main solid and fluid inclusion populations are observed: primary mixed CO₂+H₂O inclusions + Al₂SiO₅ ± brines in garnet (type 1); early CO₂-rich inclusions (± brines) in quartz (type 2); early CO₂+CH₄ (up to 4 mol%)±H₂O inclusions + graphite + fibrolite in quartz (type 3); late CH₄+CO₂+N₂ inclusions and H₂O inclusions in quartz (type 4). Densities of type 1 inclusions are consistent with the crystallization conditions of SKG (750°C and 3 kbar). The other types are post-magmatic: densities of type 2 and 3 inclusions suggest isobaric cooling at high temperature (700–550°C). Type 4 inclusions were trapped below 500°C. The SKG crystallized from a magma that was at some stage vapour-saturated; fluids were CO₂-rich, possibly with immiscible brines. CO₂-rich fluids (±brines) characterize the transition from magmatic to post-magmatic stages; progressive isobaric cooling (T<670°C) led to a continuous decrease off _{O 2} can entering in the graphite stability field; at the same time, the feldspars reacted with CO₂-rich fluids to give secondary fibrolite + graphite. Decrease ofT andf _{O 2} can explain the progressive variation in the fluid composition from CO₂-rich to CH₄ and water dominated in a closed system (in situ evolution). The presence of N₂ the late stages indicates interaction with external metamorphic fluids.Contribution within the network Hydrothermal/metamorphic water-rock interactions in crystalline rocks: a multidisciplinary approach on paleofluid analysis. CEC program: Human Capital and Mobility     

Fluid inclusion study of the Higher Himalayan quartzitic pelites, Garhwal Himalaya, India: Implications for recrystallization history of metasediments

Quartzitic pelites forms a part of Higher Himalayan Crystalline of higher geotectonic zone in Garhwal Himalaya. Quartzitic pelites (locally known as Pandukeshwar Quartzite) in Garhwal Himalaya is sandwiched between high grade metamorphic rocks of Central Crystallines and Badrinath Formation. Fluid inclusion studies are carried out on the detrital, and recrystallized quartz grains of quartzitic pelites to know about the fluid phases present during recrystallization processes at the time of maximum depth of burial. The quartzitic pelite (Pandukeshwar Quartzite) essentially consists of recrystallised quartz with accessory minerals like mica and feldspar. Fluid microthermometry study reveals the presence of three types of fluids: (i) high-salinity brine, (ii) CO₂-H₂O and (iii) H₂O-NaCl. These fluids were trapped during the development of grain and recrystallization processes. The high saline brine inclusions and CO₂-H₂O fluid with the density of 0.90 to 0.97 gm/cm³ are remnants of provenance area. CO₂ density in detrital quartz grains characterise the protolith of the sandstone as granite or metamorphic rock. The H₂O-NaCl fluids involved in the recrystallization processes at temperature-pressure of 430-350°C; 4.8 to 0.5 Kbars as constrained by fluid isochores of CO₂-H₂O and H₂O-NaCl inclusions and bulging and subgrain development during recrystallization processes. The re-equilibration of the primary fluid due to elevated internal and confining pressure is evident from features like ‘C’ shaped cavities, stretching of the inclusions, their migration and decrepitation clusters. The observed inclusion morphology revealed that the rocks were exhumed along an isothermal decompression path.     

Fluid evolution during burial and Variscan deformation in the Lower Devonian rocks of the High-Ardenne slate belt (Belgium): sources and causes of high-salinity and C–O–H–N fluids

Fluid inclusions in quartz veins of the High-Ardenne slate belt have preserved remnants of prograde and retrograde metamorphic fluids. These fluids were examined by petrography, microthermometry and Raman analysis to define the chemical and spatial evolution of the fluids that circulated through the metamorphic area of the High-Ardenne slate belt. The earliest fluid type was a mixed aqueous/gaseous fluid (H₂O–NaCl–CO₂–(CH₄–N₂)) occurring in growth zones and as isolated fluid inclusions in both the epizonal and anchizonal part of the metamorphic area. In the central part of the metamorphic area (epizone), in addition to this mixed aqueous/gaseous fluid, primary and isolated fluid inclusions are also filled with a purely gaseous fluid (CO₂–N₂–CH₄). During the Variscan orogeny, the chemical composition of gaseous fluids circulating through the Lower Devonian rocks in the epizonal part of the slate belt, evolved from an earlier CO₂–CH₄–N₂ composition to a later composition enriched in N₂. Finally, a late, Variscan aqueous fluid system with a H₂O–NaCl composition migrated through the Lower Devonian rocks. This latest type of fluid can be observed in and outside the epizonal metamorphic part of the High-Ardenne slate belt. The chemical composition of the fluids throughout the metamorphic area, shows a direct correlation with the metamorphic grade of the host rock. In general, the proportion of non-polar species (i.e. CO₂, CH₄, N₂) with respect to water and the proportion of non-polar species other than CO₂ increase with increasing metamorphic grade within the slate belt. In addition to this spatial evolution of the fluids, the temporal evolution of the gaseous fluids is indicative for a gradual maturation due to metamorphism in the central part of the basin. In addition to the maturity of the metamorphic fluids, the salinity of the aqueous fluids also shows a link with the metamorphic grade of the host-rock. For the earliest and latest fluid inclusions in the anchizonal part of the High-Ardenne slate belt the salinity varies respectively between 0 and 3.5 eq.wt% NaCl and between 0 and 2.7 eq.wt% NaCl, while in the epizonal part the salinity varies between 0.6 and 17 eq.wt% NaCl and between 3 and 10.6 eq.wt% for the earliest and latest aqueous fluid inclusions, respectively. Although high salinity fluids are often attributed to the original sedimentary setting, the increasing salinity of the fluids that circulated through the Lower Devonian rocks in the High-Ardenne slate belt can be directly attributed to regional metamorphism. More specifically the salinity of the primary fluid inclusions is related to hydrolysis reactions of Cl-bearing minerals during prograde metamorphism, while the salinity of the secondary fluid inclusions is rather related to hydration reactions during retrograde metamorphism. The temporal and spatial distribution of the fluids in the High-Ardenne slate belt are indicative for a closed fluid flow system present in the Lower Devonian rocks during burial and Variscan deformation, where fluids were in thermal and chemical equilibrium with the host rock. Such a closed fluid flow system is confirmed by stable isotope study of the veins and their adjacent host rock for which uniform δ¹⁸0 values of both the veins and their host rock demonstrate a rock-buffered fluid flow system.     

Metamorphic fluid flow in the northeastern part of the 3.8-3.7 Ga Isua Greenstone Belt (SW Greenland): A re-evalution of fluid inclusion evidence for early Archean seafloor-hydrothermal systems

Fluid inclusions in quartz globules and quartz veins of a 3.8-3.7 Ga old, well-preserved pillow lava breccia in the northeastern Isua Greenstone Belt (IGB) were studied using microthermometry, Raman spectrometry and SEM Cathodoluminescence Imaging. Petrographic study of the different quartz segregations showed that they were affected by variable recrystallization which controlled their fluid inclusion content. The oldest unaltered fluid inclusions found are present in vein crystals that survived dynamic and static recrystallization. These crystals contain a cogenetic, immiscible assemblage of CO₂-rich (+H₂O, +graphite) and brine-rich (+CO₂, +halite, +carbonate) inclusions. The gas-rich inclusions have molar volumes between 44.8 and 47.5 cm³/mol, while the brine inclusions have a salinity of ∼33 eq. wt% NaCl. Modeling equilibrium immiscibility using volumetric and compositional properties of the endmember fluids indicates that fluid unmixing occurred at or near peak-metamorphic conditions of ∼460 °C and ∼4 kbar. Carbonate and graphite were precipitated cogenetically from the physically separated endmember fluids and were trapped in fluid inclusions.In most quartz crystals, however, recrystallization obliterated such early fluid inclusion assemblages and left graphite and carbonate as solid inclusions in recrystallized grains. Intragranular fluid inclusion trails in the recrystallized grains of breccia cementing and crosscutting quartz veins have CO₂-rich assemblages, with distinctly different molar volumes (either between 43.7 and 47.5 cm³/mol or between 53.5 and 74.1 cm³/mol), and immiscible, halite-saturated H₂O-CO₂-NaCl(-other salt) inclusions. Later intergranular trails have CH₄-H₂ (X_H2 up to ∼0.3) inclusions of variable density (ranging from 48.0 to >105.3 cm³/mol) and metastable H₂O-NaCl(-other salt?) brines (∼28 eq. wt% NaCl). Finally, the youngest fluid inclusion assemblages are found in non-luminescent secondary quartz and contain low-density CH₄ (molar volume > 105.33 cm³/mol) and low-salinity H₂O-NaCl (0.2-3.7 eq. wt% NaCl). These successive fluid inclusion assemblages record a retrograde P-T evolution close to a geothermal gradient of ∼30 °C/km, but also indicate fluid pressure variations and the introduction of highly reducing fluids at ∼200-300 °C and 0.5-2 kbar. The quartz globules in the pillow fragments only contain sporadic CH₄(+H₂) and brine inclusions, corresponding with the late generations present in the cementing and crosscutting veins. We argue that due to the large extent of static recrystallization in quartz globules in the pillow breccia fragments, only these relatively late fluid inclusions have been preserved, and that they do not represent remnants of an early, seafloor-hydrothermal system as was previously proposed.Modeling the oxidation state of the fluids indicates a rock buffered system at peak-metamorphic conditions, but suggests a change towards fluid-graphite disequilibrium and a logf_H2/f_H2O above the Quartz-Fayalite-Magnetite buffer during retrograde evolution. Most likely, this indicates a control on redox conditions and on fluid speciation by ultramafic rocks in the IGB.Finally, this study shows that microscopic solid graphite in recrystallized metamorphic rocks from Isua can be deposited inorganically from a fluid phase, adding to the complexity of processes that formed reduced carbon in the oldest, well-preserved supracrustal rocks on Earth.     

The nature of fluids during pegmatite development in metamorphic terrains: Evidence from Hamadan complex,Sanandaj-Sirjan metamorphic zone,Iran

In the Sanandaj-Sirjan zone of metamorphic belt of Iran, the area south of Hamadan city comprises of metamorphic rocks, granitic batholith with pegmatites and quartz veins. Alvand batholith is emplaced into metasediments of early Mesozoic age. Fluid inclusions have been studied using microthermometry to evaluate the source of fluids from which quartz veins and pegmatites formed to investigate the possible relation between host rocks of pegmatites and the fluid inclusion types. Host minerals of fluid inclusions in pegmatites are quartz, andalusite and tourmaline. Fluid inclusions can be classified into four types. Type 1 inclusions are high salinity aqueous fluids (NaCl_eq >12 wt%). Type 2 inclusions are low to moderate salinity (NaCl_eq <12 wt%) aqueous fluids. Type 3 and 4 inclusions are carbonic and mixed CO₂-H₂O fluid inclusions. The distribution of fluid inclusions indicate that type 1 and type 2 inclusions are present in the pegmatites and quartz veins respectively in the Alvand batholith. This would imply that aqueous magmatic fluids with no detectable CO₂ were present during the crystallization of these pegmatites and quartz veins. Types 3 and 4 inclusions are common in quartz veins and pegmatites in metamorphic rocks and are more abundant in the hornfelses. The distribution of the different types of fluid inclusions suggests that CO₂ fluids generated during metamorphism and metamorphic fluids might also contribute to the formation of quartz veins and pegmatites in metamorphic terrains.     

Fluid inclusions in coesite-bearing eclogites and jadeite quartzite at Shuanghe, Dabie Shan (China)

Fluid inclusions in coesite‐bearing eclogites and jadeite quartzite at Shuanghe in Dabie Shan, East‐central China, have preserved remnants of early, prograde and/or peak metamorphic fluids, reset during post‐UHP (ultrahigh‐pressure) metamorphic uplift. Inclusions occur in several minerals (e.g. omphacite & epidote), notably as isolated, primary inclusions in quartz included in various host minerals. Two major fluid types have been identified: non‐polar fluid species (N₂ or CO₂) and aqueous, the latter is by far the most predominant. Aqueous fluids cover a wide range of salinity, from halite‐bearing brines to low salinity fluids. For non‐polar fluids, few N₂ inclusions occur in undeformed eclogite, whereas a number of CO₂‐rich inclusions have been found in microshear zones of eclogite or jadeite quartzite in close proximity to marble occurrences. The primary character of N₂ and high‐salinity aqueous inclusions indicates that they are remnants from UHP metamorphic fluids and for some there is the distinct possibility that they are ultimately derived from pre‐metamorphic fluids. This conclusion is supported by the preservation, in some samples, of microdomains containing synchronous inclusions of variable salinities, which tend to relate to the chemical composition of the host crystal. Carbonic fluids may be derived from neighbouring rocks, notably marble and carbonate‐bearing metasediments, during post‐metamorphic uplift. During post‐UHP exhumation, a limited decrease of the fluid density has occurred, with formation of new sets of fluid inclusions. Fluid movements, however, remained exceedingly limited, at the scale of the enclosing crystal.     

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.     

Fluid variability in 2 GPa eclogites as an indicator of fluid behavior during subduction

Fluid activity ratios calculated between millimeter- to centimeter-scale layers in banded mafic eclogites from the Tauern Window, Austria, indicate that variations in a _{H 2 O} existed between layers during equilibration at P approximately equal to 2GPa and T approximately equal to 625°C, whereas a _{CO 2} was nearly constant between the same layers. Model calculations in the system H₂O–CO₂–NaCl show that these results are consistent with the existence of different saturated saline brines, carbonic fluids, or immiscible pairs of both in different layers. The data cannot be explained by the exisience of water-rich fluids in all layers. The model fluid compositions agree with fluid inclusion compositions from eclogite-stage veins and segregations that contain (1) saline brines (up to 39 equivalent wt. % NaCl) with up to six silicate, oxide, and carbonate daughter phases, and (2) carbonic fluids. The formation of crystalline segregations from fluid-filled pockets or hydrofractures indicates high fluid pressures at 2 GPa; the record of fluid variability in the banded eclogite host rocks, however, implies that fluid transport was limited to local flow along individual layers and that there was no large-scale mixing of fluids during devolatilization at depths of 60–70 km. The lack of evidence for fluid mixing may, in part, reflect variations in wetting behavior of fluids of different composition; nonwetting fluids (water-rich or carbonic) would be confined to intergranular pore spaces and would be essentially immobile, whereas wetting fluids (saline brines) could migrate more easily along an interconnected fluid network. The heterogeneous distribution of chemically distinct fluids may influence chemical transport processes during subduction by affecting mineral-fluid element partitioning and by altering the migration properties of the fluid phase(s) in the downgoing slab.     

Magmatic CO2 and saline melts from the Sybille Monzosyenite,Laramie Anorthosite Complex,Wyoming

There are three populations of fluid inclusions in quartz from the Sybille Monzosyenite: early CO₂, secondary CO₂, and rare secondary brines. The oldest consist of low density CO₂ (0.70) inclusions that appear to be co-magmatic. The densities of these inclusions are consistent with the inferred crystallization conditions of the Sybille Monzosyenite, namely 3 kilobars and 950–1000° C. The other types of inclusions are secondary; they contain CO₂ (0.50) and secondary brine inclusions that form trains radiating out from a decrepitated inclusion. The sites of these decrepitated inclusions are now marked by irregularly shaped fluid inclusions and solid inclusions of salt and carbonate. Rather than fluid inclusions, feldspar contain abundant solid inclusions. These consist of magmatic minerals, hedenbergite, hornblende, ilmenite, apatite, and graphite, intimately associated with K, Na chlorides. We interpret these relations as follows: The Sybille Monzosyenite formed from a magma that contained immiscible droplets of a halide-rich melt along with a CO₂ vapor phase. The salt was trapped along with the other obvious magmatic minerals during growth of the feldspars. CO₂ may have also been included in the feldspars but it probably leaked later during exsolution of the feldspars and was not preserved. Both the saline melt and the CO₂ vapor were trapped in the quartz. The melt inclusions in the quartz later decrepitated, perhaps due to progressive exsolution of fluids, to produce the secondary H₂O and CO₂ inclusions. These observations indicate that the Sybille Monzosyenite, which is a markedly anhydrous rock, was actually vapor-saturated. Rather than being H₂O, however, the vapor was CO₂-rich and possibly related to an immiscible chloride-rich melt.     

Retrograde mineral and fluid evolution in high-pressure metapelites (Schistes lustrés unit, Western Alps)

Fluid inclusions have been analysed in successive generations of syn-metamorphic segregations within low-grade, high-pressure, low-temperature (HP–LT) metapelites from the Western Alps. Fluid composition was then compared to mass transfer deduced from outcrop-scale retrograde mineral reactions. Two types of quartz segregations (veins) occur in the `Schistes lustrés' unit: early blueschist-facies carpholite-bearing veins (BS) and retrograde greenschist-facies chlorite-bearing veins (GS). Fluid inclusions in both types of segregations are aqueous (no trace of dissolved gases such as CO₂, CH₄, N₂), with significant differences in density and composition (salinity). BS fluids are moderately saline fluids (average 9.1 wt% eq. NaCl) characterized by a chronological trend towards more dilute composition (from 15 down to 0 wt% eq. NaCl), whereas GS fluids have a very constant salinity of ∼3.7 wt% eq. NaCl. Both types of inclusions were continuously reset to lower densities along the retrograde path, until a temperature of ∼300 °C. Mass-balance calculations, together with fluid inclusion data, suggest that GS fluids result from the mixing between two fluid sources: one initial, early metamorphic, moderately saline HP fluid and a second nearly pure water fluid provided by the breakdown of carpholite. Estimates of the amount of water released by carpholite breakdown result in a dilution of the interstitial fluid phase (from 10 to 2.5–4 wt% eq. NaCl) consistent with the actual shift of the fluid composition. Alkali elements required for the formation of the GS chlorite + phengite assemblage after carpholite could be locally provided by HP phengite. This is taken as an indirect evidence that, during the generation of both BS and GS fluids, mixing with externally derived fluids may have been very limited. The location, amount and constant composition of the less saline GS fluids appear to be related to an interconnected porosity at the time of inclusion formation. Received: 19 October 1998 / Accepted: 19 July 2000     

Pressure-temperature and evolution of fluid compositions of Al2SiO5-bearing rocks,Mica Creek,B.C., in light of fluid inclusion data and mineral equilibria

Metamorphosed pelitic rocks from Mica Creek, British Columbia contain sillimanite, kyanite with minor fibrolite and andalusite-bearing quartz pods. Mineral equilibria were used to infer peak P-T conditions and fluid compositions in equilibrium with the solid phases. Fluid inclusions in three schist samples appear to be good indicators of conditions affecting those rocks during and after peak metamorphic conditions. In samples from two localities, fluid inclusions from schist and quartz-rich segregations have densities appropriate to the peak metamorphic conditions. The observed compositions for these fluids (low salinity with 12 mole % dissolved CO₂) agree with calculated values of 0.84 to 0.85, based upon paragonite-quartz-albite-Al₂SiO₅ equilibria. The fluids unmixed as the schists were uplifted and cooled; fluid inclusions trapped during this stage outline a solvus in the CO₂-H₂O-NaCl system. A later influx of fluids containing CH₄ and N₂ accompanied formation of andalusite-bearing plagioclaserich segregations. The restricted association of andalusite-bearing pods and low density fluids suggest a localized but pervasive fluid influx during uplift. Preservation of high density fluid inclusions during uplift and erosion, coupled with evidence for unmixing of H₂O- and CO₂-rich fluids on the solvus, provide constraints on the P-T uplift path.     

Fluid entrapment and reequilibration during subduction and exhumation: A case study from the high-grade Nestos shear zone, Central Rhodope, Greece

A fluid inclusion study on metamorphic minerals of successive growth stages was performed on highly deformed paragneisses from the Nestos Shear Zone at Xanthi (Central Rhodope), in which microdiamonds provide unequivocal evidence for ultrahigh-pressure (UHP) metamorphism. The correlation of fluid inclusion density isochores and fluid inclusion reequilibration textures with geothermobarometric data and the relative chronology of micro- and macro-scale deformation stages allow a better understanding of both the fluid and metamorphic evolution along the P–T–d path. Textural evidence for subduction towards the NE is recorded by the orientation of intragranular NE-oriented fluid inclusion planes and the presence of single, annular fluid inclusion decrepitation textures. These textures occur within quartz “foam” structures enclosed in an earlier generation of garnets with prolate geometries and rarely within recrystallized matrix quartz, and reequilibrated both in composition and density during later stages of exhumation. No fluid inclusions pertaining to the postulated ultrahigh-pressure stage for microdiamond-bearing garnet–kyanite–gneisses have yet been found. The prolate shape of garnets developed during the earliest stages of exhumation that is recorded structurally by (L  S) tectonites, which subsequently accommodated progressive ductile SW shearing and folding up to shallow crustal levels. The majority of matrix kyanite and a later generation of garnet were formed during SW-directed shear under plane-strain conditions. Fluid inclusions entrapped in quartz during this stage of deformation underwent density loss and transformed to almost pure CO₂ inclusions by preferential loss of H₂O. Those inclusions armoured within garnet retained their primary 3-phase H₂O–CO₂ compositions. Reequilibration of fluid inclusions in quartz aggregates is most likely the result of recrystallization along with stress-induced, preferential H₂O leakage along dislocations and planar lattice defects which results in the predominance of CO₂ inclusions with supercritical densities. Carbonic fluid inclusions from adjacent kyanite–corundum-bearing pegmatoids and, the presence of shear-plane-parallel fluid inclusion planes within late quartz boudin structures consisting of pure CO₂-fluid inclusions with negative crystal shapes, bear witness of the latest stage of deformation by NE-directed extensional shear.This study shows that the textures of early fluid inclusions that formed already during the prograde metamorphic path can be preserved and used to derive information about the kinematics of subduction that is difficult to obtain from other sources. The textures of early inclusions, together with later generations of unaltered primary and secondary inclusions in metamorphic index minerals that can be linked to specific deformation stages and even P–T conditions, are a welcome supplement for the reconstruction of a rather detailed P–T–d path.     

Composition and origin of fluids associated with lode gold deposits in a Mesoarchean greenstone belt (Warrawoona Syncline, Pilbara Craton, Western Australia) using synchrotron radiation X-ray fluorescence

Microthermometry and Raman spectroscopy techniques are routinely use to constrain ore-fluids δ¹⁸O and molar proportions of anhydrous gas species (CO₂, CH₄, N₂). However, these methods remain imprecise concerning the ore-fluids composition and source. Synchrotron radiation X-ray fluorescence allows access to major and trace element concentrations (Cl, Br and K, Ca, Fe, Cu, Zn, As, Rb, Sr) of single fluid inclusion. In this paper, we present the results of the combination of these routine and newly developed techniques in order to document the fluids composition and source associated with a Mesoarchaean lode gold deposit (Warrawoona Syncline, Western Australia). Fluid inclusion analyses show that quartz veins preserved records of three fluid inclusion populations. Early fluids inclusions, related to quartz veins precipitation, are characterized by a moderate to high Br/Cl ratio relative to modern seawater, CO₂ ± CH₄ ± N₂, low to moderate salinities and significant base metal (Fe, Cu, Zn) and metalloid (As) concentrations. Late fluid inclusions trapped in secondary aqueous fluid inclusions are divided into two populations with distinct compositions. The first population consists of moderately saline aqueous brines, with a Br/Cl ratio close to modern seawater and a low concentration of base metals and metalloids. The second population is a fluid of low to moderate salinity, with a low Br/Cl ratio relative to modern seawater and significant enrichment in Fe, Zn, Sr and Rb. These three fluid inclusion populations point to three contrasting sources: (1) a carbonic fluid of mixed metamorphic and magmatic origin associated with the gold-bearing quartz precipitation; (2) a secondary aqueous fluid with seawater affinity; and (3) a surface-derived secondary aqueous fluid modified through interaction with felsic lithologies, before being flushed into the syncline. Primary carbonic fluids present similar characteristics than those ascribed to Mesoarchaean lode gold deposits. This suggests similar mineralization processes for mid- and Mesoarchaean lode gold deposits despite contrasting fluid–rock interaction histories. However, in regard to the protracted history documented in the Warrawoona Syncline, we question the robustness of the epigenetic crustal continuum model, as ore-fluid characteristics equally support an epigenetic or a polyphased mineralization process.     

Graphite-bearing CO2-fluid inclusions in granulites: Insights on graphite precipitation and carbon isotope evolution

Graphite in deep crustal enderbitic (orthopyroxene + garnet + plagioclase + quartz) granulites (740°C, 8.9 kb) of Nilgiri hills, southern India were investigated for their spectroscopic and isotopic characteristics. Four types of graphite crystals were identified. The first type (Gr_I), which is interstitial to other mineral grains, can be grouped into two subtypes, Gr_IA and Gr_IB. Gr_IA is either irregular in shape or deformed, and rough textured with average δ¹³C values of −12.7 ± 0.4‰ (n = 3). A later generation of interstitial graphite (Gr_IB) shows polygonal crystal shapes and highly reflecting smooth surface features. These graphite grains are more common and have δ¹³C values of −11.9 ± 0.3‰ (n = 14). Both subtypes show well-defined Raman shifts suggesting a highly crystalline nature. Cores of interstitial graphite grains have, on average, lower δ¹³C values by ∼0.5‰ compared to that of the rim. The second type of graphite (Gr_II) occurs as solid inclusions in silicate minerals, commonly forming regular hexagonal crystals with a slightly disordered structure. The third type of graphite (Gr_III) is associated with solid inclusions (up to 100 μm) that have decrepitation halos of numerous small (<15 μm) satellite fluid inclusions of pure CO₂ with varying density (1.105 to 0.75 g/cm³). The fourth type of graphite (Gr_IV) is found as daughter crystals within primary type CO₂-fluid inclusions in garnet and quartz. These fluid inclusions have a range of densities (1.05 to 0.90 g/cm³), but in general are significantly less dense than graphite-free primary, pure CO₂ fluid inclusions (1.12 g/cm³). Raman spectral characteristics of graphite inside fluid inclusions suggest graphite crystallization at low temperature (∼ 500°C). The precipitation of graphite probably occurred during the isobaric cooling of CO₂-rich peak metamorphic fluid as a result of oxyexsolution of oxide phases. The oxyexsolution process is evidenced by the magnetite-ilmenite granular exsolution textures and the systematic presence of numerous micron-sized rutile and other oxide inclusions in association with fluid inclusions within garnet, plagioclase, and quartz.The carbon isotope compositions of coexisting CO₂ (in fluid inclusions) and graphite show a fractionation (α₂CO−gr) of ∼6‰ in garnet, consistent with the existing theoretical estimates of α₂CO−gr at 800°C. A subsequent generation of CO₂ inclusions trapped in matrix quartz and quartz segregation have higher δ¹³C values, −4‰ and −2.9‰ respectively. Graphite in quartz segregations also has higher δ¹³C values (−9.8‰) than those in enderbite (−12.7‰). Micro-graphite crystals included in garnet, quartz (enderbite), and quartz (segregation) have average δ¹³C values of −11.1, −10.4, and −8.7‰ respectively, indicating progressive enrichment in ¹³C with a decrease in temperature of recrystallization of respective minerals. This progressive enrichment is also observed in carbon isotope compositions of fluid inclusion CO₂, suggesting isotopic equilibrium during graphite precipitation from CO₂ fluids. Thus, the carbon isotope record preserved in these rocks by the interstitial graphite, CO₂ fluid in enderbite, graphite microcrystals, graphite in quartz segregation, and CO₂ fluid in quartz segregation, suggests a temperature-controlled isotopic evolution. This evolution is in accordance with a closed system Rayleigh-type graphite precipitation process which progressively enriched residual CO₂ in ¹³C.     

Ore-forming fluids associated with granite-hosted gold mineralization at the Sanshandao deposit, Jiaodong gold province, China

The Sanshandao gold deposit, with total resources of more than 60 t of gold, is located in the Jiaodong gold province, the most important gold province of China. The deposit is a typical highly fractured and altered, disseminated gold system, with high-grade, quartz-sulphide vein/veinlet stockworks that cut Mesozoic granodiorite. There are four stages of veins that developed in the following sequence: (1) quartz-K-feldspar-sericite; (2) quartz-pyrite±arsenopyrite; (3) quartz-base metal sulfide; and (4) quartz-carbonate. Fluid inclusions in quartz and calcite in vein/veinlet stockworks contain C-O-H fluids of three main types. The first type consists of dilute CO₂–H₂O fluids coeval with the early vein stage. Molar volumes of these CO₂–H₂O fluid inclusions, ranging from 50–60 cm³/mol, yield estimated minimum trapping pressures of 3 kbar. Homogenization temperatures, obtained mainly from CO₂–H₂O inclusions with lower CO₂ concentration, range from 267–375 °C. The second inclusion type, with a CO₂–H₂O±CH₄ composition, was trapped during the main mineralizing stages. These fluids may reflect the CO₂–H₂O fluids that were modified by fluid/rock reactions with altered wallrocks. Isochores for CO₂-H₂O±CH₄ inclusions, with homogenization temperatures ranging from 204–325 °C and molar volumes from 55 to 70 cm³/mol, provide an estimated minimum trapping pressure of 1.2 kbar. The third inclusion type, aqueous inclusions, trapped in cross-cutting microfractures in quartz and randomly in calcite, are post-mineralization, and have homogenization temperatures between 143–228 °C and salinities from 0.71–7.86 wt% NaCl equiv. Stable isotope data show that the metamorphic fluid contribution is minimal and that ore fluids are of magmatic origin, most likely sourced from 120–126 Ma mafic to intermediate dikes. This is consistent with the carbonic nature of the fluid, and the cross-cutting nature of those deposits relative to the host Mesozoic granitoid.Editorial handling: R.J. Goldfarb     

Fluid composition and evolution in coesite-bearing rocks (Dora-Maira massif,Western Alps): implications for element recycling during subduction

Fluid inclusions and F, Cl concentration of hydrous minerals were analysed in the coesite-pyrope quartzite, the interlayered jadeite quartzite and their country-rock gneiss from the Dora-Maira massif using a combination of microthermometry, Raman spectrometry, synchrotron X-ray microfiuorescence and electron microprobe analysis. Three populations of fluid inclusions were recognized texturally and can be related to distinct metamorphic stages. A low-salinity aqueous fluid occurs in the retrogressed country gneiss and as late secondary inclusions in jadeite quartzite and chloritized pyrope. An earlier secondary population is found in matrix quartz of the jadeite- and pyro-pe-quartzites. This population can be related to the early decompression and so to incipient breakdown of garnet into phlogopite-bearing assemblages. The inclusion fluid is highly saline (up to 84 wt% equivalent NaCl) and contains Na, Ca, Fe, Cu and Zn as major cations. In pyrope quartzite, additional K was found in these brines, which locally coexist with CO₂-rich inclusions. The oldest fluid inclusions are preserved in kyanite grains included in fresh pyrope and in pyrope itself. In pyrope, all inclusions have decrepitated and contain magnesite, an Mg-phosphate, sheet-silicate(s), a chloride and an opaque phase, with no fluid preser ved. In contrast, the kyanite inclusions in pyrope preserve primary H₂O-CO₂ low-salinity fluid inclusions, probably owing to the low compressibility of the kyanite inclusions and host garnet. In spite of in-situ re-equilibration, these inclusions can be interpreted as relics of the dehydration fluid that attended pyrope growth. These correlations between textural and chemical fluid inclusion data and metamorphic stages are consistent with the fluid composition calculated from the halogen content of different generations of phlogopite and biotite. The preservation of different fluid compositions, both in time and space, is evidence for local control and possibly origin of the fluids, in agreement with isotopic data. These results, in particular the absence of CO₂ in the jadeite quartzite, are best interpreted in terms of a fluid-melt system evolution. With increasing metamorphism, partitioning of H₂O, Na, Ca, Fe and heavy metals into melt (jadeite quartzite) and Mg, Na/K, F, CO₂ and P(?) into a residual aqueous fluid can account for depletion in Na, Ca and Fe of the pyrope quartzite. During the retrograde path, a _{H 2 O} rose as melt crystallized, generating the two populations of hypersaline and water-rich fluids that were highly reactive to pyrope. The process of fluid-melt interaction envisioned here coupled with models of melt extraction in subduction zones provides an attractive opportunity for the instantaneous ( < 1 Ma) and selective transport of elements between a downgoing slab and the overlying mantle wedge.     

Remnants of premetamorphic fluid and oxygen isotopic signatures in eclogites and garnet clinopyroxenite from the Dabie-Sulu terranes, eastern China

A combined oxygen‐isotope and fluid‐inclusion study has been carried out on high‐ and ultrahigh‐pressure metamorphic (HP/UHPM) eclogites and garnet clinopyroxenite from the Dabie‐Sulu terranes in eastern China. Coesite‐bearing eclogites/garnet clinopyroxenite and quartz eclogites have a wide range in whole‐rock δ¹⁸O_VSMOW, from 0 to 11‰. The high‐T oxygen‐isotope fractionations preserved between quartz and garnet preclude significant retrograde isotope exchange during exhumation, and the wide range in whole‐rock oxygen‐isotope composition is thought to be a presubduction signature of the precursors. Aqueous fluids with variable salinities and gas species (N₂‐, CO₂‐, or CH₄‐rich), are trapped as primary inclusions in garnet, omphacite and epidote, and in quartz blebs enclosed within eclogitic minerals. In high‐δ¹⁸O HP/UHPM rocks from Hujialin and Shima, high‐salinity brine and/or N₂ inclusions occur in garnet porphyroblasts, which also contain inclusions of coesite, Cl‐rich blue amphibole and dolomite. In contrast, in low‐δ¹⁸O eclogites from Qinglongshan and Huangzhen, the Cl concentrations in amphibole are very low, < 0.2 wt.%, and low‐salinity aqueous inclusions occur in quartz inclusions in epidote porphyroblasts and in epidote cores. These low‐salinity fluid inclusions are believed to be remnants of meteoric water, although the fluid composition was modified during pre‐ and syn‐peak HP/UHPM. Eclogites at Houshuichegou and Hetang contain CH₄‐rich fluid inclusions, coexisting with high‐salinity brine inclusions. Methane was probably formed under the influence of CO₂‐rich aqueous fluids during serpentinisation of mantle‐derived peridotites prior to or during plate subduction. Remnants of premetamorphic low‐ to high‐salinity aqueous fluid with minor N₂ and/or other gas species preserved in the Dabie‐Sulu HP/UHPM eclogites and garnet clinopyroxenite indicate a great diversity of initial fluid composition in the precursors, implying very limited fluid–rock interaction during syn‐ and post‐peak HP/UHPM.     

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     

The nature of the fluids associated with the Monte Rosa gold district, NW Alps, Italy

Recent O-isotope and fluid inclusion studies have provided evidence on the nature of the fluids associated with the late-Alpine quartz-gold deposits of the Monte Rosa district. The most abundant inclusions in quartz from these deposits contain a low salinity aqueous fluid (about 2% to 10% wt. NaCl eq.), and a CO₂ phase (usually less than 20% mol), in places with minor methane. CO₂ densities and total homogenization temperatures vary widely throughout the district, reflecting diverse conditions of trapping (P = 1 to 3 kb, T = 300° to 450°C). At Miniera dei Cani, unmixing between CO₂-rich and H₂O-rich fluids possibly occurred. A second type of inclusion contains an aqueous brine without recognizable CO₂, and is especially abundant at Val Toppa. O-isotope studies suggest that fluids were largely equilibrated in a metamorphic environment. It is concluded that the gold-related fluids in the district were mainly of a metamorphic nature; at Val Toppa, both isotopic and fluid inclusion data point to contributions of unexchanged meteoric waters. Mechanisms of gold transport and precipitation are less contrained. A possible model involves transport of gold as bisulfide complexes, and precipitation due to one or more of the following processes: decrease of sulfur activity due to precipitation of sulfides, wall-rock reaction, cooling/dilution, and/or fluid unmixing.