Submicron-sized fluid inclusions and distribution of hydrous components in jadeite,quartz and symplectite-forming minerals from UHP jadeite–quartzite in the Dabie Mountains,China: TEM and FTIR investigation

Fluid inclusions and clusters of water molecules at nanometer-to submicron-scale in size have been investigated using transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR) in jadeite, quartz and symplectite aegirine–augite, albite, taramite and magnetite corona minerals from ultrahigh-pressure (UHP) jadeite–quartzite at Shuanghe, the Dabie Mountains, China. Fluid inclusions from 0.003 μm to 0.78 μm in size occur in jadeite and quartz crystals, and a small number of fluid inclusions from 0.001 μm to 0.25 μm have also been detected in symplectite-forming minerals. Most of the fluid inclusions have round or negative crystal morphology and contain aqueous fluids, but some contain CO₂-rich fluids. They are usually connected to dislocations undetectable at an optical scale. The dislocations represent favorable paths for fluid leakage, accounting for non-decrepitation of most fluid inclusions when external pressure decreased at later stages, although there was partial decrepitation of some fluid inclusions unconnected to defect microstructures resulting from internal overpressure. Non-decrepitation and partial decrepitation of fluid inclusions resulted in changes of original composition and/or density. It is clear that identification of hidden re-equilibration features has significant implications for the petrological interpretation of post-peak metamorphic processes. Micro-FTIR results show that all jadeite and quartz samples contain structural water occurring as hydroxyl ions (OH⁻) and free water (H₂O) in the form of clusters of water molecules. The H₂O transformed from OH⁻ during exhumation and could have triggered and enhanced early retrograde metamorphism of the host rocks and facilitated plastic deformation of jadeite and quartz grains by dislocation movement, and thus the H₂O released during decompression might represent early-stage retrograde metamorphic fluid. The nominally anhydrous mineral (NAM) jadeite is able to transport aqueous fluids in concentrations of at least several hundred ppm water along a subduction zone to mantle depths in the form of clusters of water molecules and hydroxyl ions within crystals.     

Synthetic fluid inclusions - VII. Re-equilibration of fluid inclusions in quartz during laboratory-simulated metamorphic burial and uplift

ABSTRACT P-T conditions inferred from fluid inclusions in metamorphic rocks often disagree with the values predicted from mineral equilibria calculations. These observations suggest that inclusions formed during early stages of regional metamorphism continue to re-equilibrate during burial and subsequent uplift in response to differential pressure. P-T conditions accompanying burial and uplift were experimentally simulated by initially forming pure H₂O inclusions in quartz at elevated temperatures and pressures, and then re-equilibrating the inclusions in the presence of a 20 wt% NaCl solution such that final confining pressures ranged from 5 kbar above to 4 kbar below the initial internal pressure of the inclusions at the temperature of re-equilibration. In all samples re-equilibrated at confining pressures below the internal pressure, some inclusions were formed that had compositions of 20 wt% NaCl and densities in accord with the final P-T conditions. Additionally, some inclusions were observed to contain fluids of intermediate salinities (between 0 and 20 wt% NaCl). Densities of these inclusions were also consistent with formation at the re-equilibration P-T conditions. The remainder of the fluid inclusions observed in these samples contained pure H₂O and their homogenization temperatures corresponded to densities intermediate between the initial and final P-T conditions. In short-term experiments (7 days) where the initial internal overpressure exceeded 1 kbar, no inclusions were found that contained the original density and none were found to have totally re-equilibrated. Instead, most H₂O inclusions re-equilibrated until their internal pressures were between ∼750 and 1500 bars above the confining pressure, regardless of the initial pressure differential. In a long-term experiment (52 days), inclusions re-equilibrated at a lower confining pressure than the initial internal pressure displayed homogenization temperatures corresponding to a range in final internal pressures between 0 kbar (i.e. total re-equilibration) and 1.2 kbar above the confining pressure. In experiments where the confining pressure during re-equilibration exceeded the initial internal pressure, densities of pure H₂O inclusions increased to values intermediate between the initial and final P-T conditions. Additionally, these inclusions were generally surrounded by a three-dimensional halo of smaller inclusions, also of intermediate density, resulting in a texture similar to that previously ascribed to decrepitation from internal overpressure. In extreme cases where confining pressures were 4–5 kbar above the initial pressure, the parent inclusion almost completely closed leaving only the three-dimensional array of small (5 μm) inclusions, the outline of which may be several times the volume of the original inclusion. Groups of such inclusions closely resemble textures commonly observed in medium- to high-grade metamorphic rocks. Inclusions containing 10 and 42 wt% NaCl solutions trapped at 600 °c and 3 kbar were re-equilibrated at 600 °c and 1 kbar for 5 days in dry argon to evaluate the importance of H₂O diffusion as a mechanism of lowering the inclusion bulk density. Salinities of re-equilibrated inclusions obtained from freezing point depressions and halite dissolution temperatures indicate that original compositions were preserved. Density changes similar to those previously described were noted in these experiments, in inclusions showing no visible microfractures. Therefore, density variations observed in inclusions in this study, re-equilibrated under rapid deformation conditions, are considered to result from a change in the inclusion volume, without significant loss of contents by diffusion or leakage.     

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.     

Retrograde fluid evolution at the Rampura Agucha Pb-Zn-(Ag) deposit, Rajasthan, India

Fluid inclusions in mineralized graphite-sillimanite-mica schist from the Rampura-Agucha Pb-Zn-(Ag) deposit, Rajasthan, northwest India, have been investigated by microthermometry and Raman microspectrometry. Three different main types of fluid inclusions in quartz can be distinguished: (1) gaseous (CO₂, partially mixed with CH₄-N₂), (2) low salinity aqueous inclusions (0–8 eq. wt% NaCl) and (3) high salinity aqueous inclusions (NaCl ± MgCl₂-CaCl₂). Low density CO₂-rich and low salinity H₂O inclusions are contemporaneous and occur, together with CH₄-N₂ inclusions, in close association with sulfide mineral inclusions. This indicates immiscibility between the gaseous and aqueous phase and participation of these fluids during the deposition or remobilization of the ore, which occurred over a wide P (1220 to 200 bar) and T (450 to 250 °C). Raman spectra of graphite indicate upper greenschist-facies metamorphic conditions, although host rocks have been metamorphosed at upper amphibolite-facies metamorphic conditions. This indicates that graphite re-equilibrated with the CO₂-rich phase during retrograde metamorphism.     

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.     

Primary to re-equilibrated fluids and geochemical signatures for the evolution of the Nagthat siliciclastics in the Tons valley,Lesser Himalaya,India

Medium to coarse-grained Neo-Proterozoic Nagthat siliciclastic rocks form a part of the Krol Formation in the Lesser Himalayan geotectonic zone. Fluid inclusion and geochemical studies have been carried out on the Nagthat siliciclastics from the Tons valley to determine their provenance during the Proterozoic and their recrystallisation during maximum burial to uplift. Fluid inclusion studies have been carried out on detrital, recrystallised quartz grains and quartz overgrowths. Major and trace element analyses of the siliciclastics, the relationships of SiO₂ with various trace elements, and the association of various trace elements with mineral species suggest a granitic source for these siliciclastics. Primary Q1 aqueous brine inclusions and Q3 H₂O–CO₂ fluid with 0.9 gm/cm³ CO₂ density in detrital quartz grains characterised the protolith of the sandstone as granite or metamorphic rocks. H₂O–NaCl fluids participated in the cementation history, temperatures of quartz overgrowth from 198 to 232 °C show the effect of maximum burial. The re-equilibration of the primary fluid due to elevated internal pressure > confining pressure is evident from features like ‘C’ shaped cavities, stretching of the inclusions, their migration, decrepitation clusters, etc. During recrystallisation these inclusions were equilibrated at 187 ° and 235 °C in a restricted fluid of aqueous, moderately saline composition. The observed inclusion morphology is attributed to a decrease in external pressure related to isothermal decompression uplift.     

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     

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     

Metamorphic and post-metamorphic fluid flow in the low-grade rocks of the Harlech Dome, north Wales

A combination of fluid inclusion, stable isotope and geochemical techniques has been used to study the nature of fluids present and their behaviour during Caledonian low-grade metamorphism of the Harlech Dome, north Wales. Fluid inclusion studies show that in most of the metasedimentary sequence the peak metamorphic fluid was an aqueous Na–K–Cl brine but in the graphitic Clogau Formation and in parts of the overlying Maentwrog Formation immiscible H₂O-rich and CH₄-rich fluids coexisted. Late-stage inclusions are of calcium-rich brine and a dilute aqueous fluid. The chemical composition of chlorite in metamorphic veins and rocks varies between different formations and quartz-oxygen isotopic compositions show considerable variation between different units. Both of these features are taken to indicate that there was little or no pervasive movement of fluid between different units at the peak of metamorphism. After the metamorphic peak there was focused flow of fluid upward through the sequence along fractures, in response to end-Caledonian uplift and unloading. Where the migrating fluid crossed the graphitic shales, interaction between the fluid and the shales gave rise to the formation of the auriferous veins of the Dolgellau Gold Belt. Subsequent to this mineralizing event there was widespread development of ¹⁸O-enriched calcites and micas. In the case of vein minerals it is possible that these crystallized directly from late-stage fluids at lower temperature than the quartz in the same veins. Alternatively, the original vein minerals may have re-equilibrated with later ¹⁸O-enriched or cooler fluid. In the case of muscovites in the rock matrix it is proposed that the isotopically heavy compositions are the result of re-equilibration of initially light grains with an introduced fluid, requiring considerable influx of fluid. This event may relate to either of two late-stage fluids observed as inclusions.     

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 evolution in the Pote Shear Zone Harare-Shamva-Bindura greenstone belt (northeast Zimbabwe)

A fluid inclusion study was completed on syn-deformational quartz veins of the Pote River Shear Zone, which is situated on the border between the Harare-Bindura greenstone belt and the granitoids of the Chinamora Batholith. The fluid inclusions were studied by means of microthermometry and Laser-Raman microspectrometry. The fluid inclusions consist of three major compositional types: (1) H₂OCO₂±N₂±halite inclusions in clusters and trails; (2) H₂OCO₂ inclusions (H₂O = 30–60 vol. %) in trails; and (3) H₂O-halite inclusions in trails. These fluid generations are explained by trapping at different P-T conditions of two different fluids: a high salinity aqueous fluid and a low salinity H₂OCO₂ fluid with XH₂O around 0.8. High salinity aqueous fluid inclusions are characteristic for the granite-greenstone contact and are absent within the Harare-Shamva-Bindura greenstone belt. The high salinity aqueous fluid has, therefore, been interpreted as magmatic in origin. The low salinity H₂OCO₂ fluid is most likely metamorphic in origin.     

Thermal metamorphism and H2O-CO2-NaCl immiscibility at Patapedia,Quebec: evidence from fluid inclusions

The methamorphic history of the Patapedia thermal zone, Gaspé, Quebec, is re-evaluated in the light of results obtained from a study of fluid inclusions contained in quartz phenocrysts of felsic dyke rocks. The thermal zone is characterised by calc-silicate bodies that have outwardly telescoping prograde metamorphic isograds and display extensive retrograde metamorphism with associated copper mineralization. Three distinct fluid inclusion types are recognized: a low to moderate salinity, high density aqueous fluid (Type I); a low density CO₂ fluid (Type II); and a high salinity, high density aqueous fluid (Type III). Fluid inclusion Types I and II predominate whereas Type III inclusions form <10% of the fluid inclusion population. All three fluid types are interpreted to have been present during prograde metamorphism. Temperatures and pressures of metamorphism estimated from fluid inclusion microthermometry and isochore calculations are 450°–500° C and 700–1000 bars, respectively. A model is proposed in which the metamorphism at Patapedia was caused by heat transferred from a low to moderate salinity fluid of partly orthomagmatic origin (Type I inclusions). During the early stages, and particularly in the deeper parts of the system, CO₂ produced by metamorphism was completely miscible in the aqueous hydrothermal fluid and locally resulted in high XCO₂ fluids. On cooling and/or migrating to higher levels these latter fluids exsolved high salinity aqueous fluids represented by the Type III inclusions. Most of the metamorphism, however, took place at temperature-pressure conditions consistent with the immiscibility of CO₂ and the hydrothermal fluid and was consequently accompanied by the release of large volumes of CO₂ vapour which is represented by Type II inclusions. The final stage of the history of the Patapedia aureole was marked by retrograde metamorphism and copper mineralization of a calcite-free calc-silicate hornfels in the presence of a low XCO₂ fluid.     

CO2-Brine immiscibility at high temperatures,evidence from calcareous metasedimentary rocks

Study of fluid inclusions in quartz segregations and in the rock matrix of a calcareous psammite and a carbonate schist suggests that brines containing 23–24 weight percent salt (NaCl equivalent) are immiscible with CO₂ at the metamorphic conditions of approximately 600° and 6.5 Kb. The presence of a high temperature solvus between saline brine and CO₂ is supported by other fluid inclusion studies as well as experimental measurements from the literature. As saline brines are common in metamorphic and hydrothermal systems, CO₂-brine immiscibility should play an important role in petrogenesis. The fluid inclusions preserved in the quartz segregations probably represent the fluids generated by prograde metamorphic reactions, whereas the compositions of the fluids trapped in the rock matrix quartz suggest they have reequilibrated with the matrix minerals during incipient retrograde reactions. The isochores from the densest inclusions observed in this study pass close to the inferred peak metamorphic conditions; other isochores suggest an episode of deformation and recrystallization at 275° C and 1.4 Kb. Using the density information preserved in all the inclusions, a convex-downward uplift path on a P-T diagram is inferred for these rocks.     

Origin of CO2-rich fluid inclusions in synorogenic veins from the Eastern Mount Isa Fold Belt, NW Queensland, and their implications for mineralization

Synorogenic veins from the Proterozoic Eastern Mount Isa Fold Belt contain three different types of fluid inclusions: CO₂-rich, aqueous two-phase and rare multiphase. Inclusions of CO₂ without a visible H₂O phase are particularly common. The close association of CO₂-rich inclusions with aqueous two-phase, and possibly multiphase inclusions suggests that phase separation of low- to -moderate salinity CO₂-rich hydrothermal fluids led to the selective entrapment of the CO₂. Microthermometric results indicate that CO₂-rich inclusions homogenize between –15.5 and +29.9 °C which corresponds to densities of 0.99 to 0.60 g.cm⁻³. The homogenization temperatures of the associated aqueous two-phase inclusions are 127–397 °C, with salinities of 0.5 to 18.1 wt.% NaCl equivalent. The rarely observed multiphase inclusions homogenize between 250 and 350 °C, and have salinities ranging from 34.6 to 41.5 wt.% NaCl equivalent. Evidence used to support the presence of fluid immiscibility in this study is mainly derived from observations of coexisting H₂O-rich and CO₂-rich inclusions in groups and along the same trail. In addition, these two presumably unmixed fluids are also found on adjacent fractures where monophase CO₂-rich inclusions are closely related to H₂O-rich inclusions. Similar CO₂-rich inclusions are widespread in mineral deposits in this region, which are simply metal-enriched synorogenic veins. Therefore, we argue that fluid immiscibility caused volatile species such as CO₂ and H₂S to be lost from liquid, thus triggering ore deposition by increasing the fluid pH and decreasing the availability of complexing ligands. Received: 28 April 1997 / Accepted: 4 January 1999     

Fluid inclusion characteristics of mesothermal gold deposits in the Xiaoqinling district, Shaanxi and Henan Provinces, People's Republic of China

Fluid inclusions were studied in quartz samples from early (stage I) gold-poor quartz veins and later (stage II) gold- and sulphide-rich quartz veins from the Wenyu, Dongchuang, Qiangma, and Guijiayu mesothermal gold deposits in the Xiaoqinling district, China. Fluid inclusion petrography, microthermometry, and bulk gas analyses show remarkably consistent fluid composition in all studied deposits. Primary inclusions in quartz samples are dominated by mixed CO₂-H₂O inclusions, which have a wide range in CO₂ content and coexist with lesser primary CO₂-rich and aqueous inclusions. In addition, a few secondary aqueous inclusions are found along late-healed fractures. Microthermometry and bulk gas analyses suggest hydrothermal fluids with typically 15–30 mol% CO₂ in stage I inclusions and 10–20 mol% CO₂ in stage II inclusions. Estimates of fluid salinity decrease from 7.4–9.2 equivalent wt.% NaCl to 5.7–7.4 equivalent wt.% NaCl between stage I and II. Primary aqueous inclusions in both stages show consistent salinity with, but slightly lower Th _total than, their coexistent CO₂-H₂O inclusions. The coexisting CO₂-rich, CO₂-H₂O, and primary aqueous inclusions in both stage I and II quartz are interpreted to have been trapped during unmixing of a homogeneous CO₂-H₂O parent fluid. The homogenisation temperatures of the primary aqueous inclusions give an estimate of trapping temperature of the fluids. Trapping conditions are typically 300–370 °C and 2.2 kbar for stage I fluids and 250–320 °C and 1.6 kbar for stage II fluids. The CO₂-H₂O stage I and II fluids are probably from a magmatic source, most likely devolatilizing Cretaceous Yanshanian granitoids. The study demonstrates that gold is largely deposited as pressures and temperatures fall accompanying fluid immiscibility in stage II veins. Received: 15 May 1997 / Accepted: 10 June 1998     

Fluid inclusion modification by H2O and D2O diffusion: the influence of inclusion depth, size, and shape in re-equilibration experiments

The mobility of H₂O and D₂O by diffusion through quartz is illustrated with H₂O-rich fluid inclusions synthesized at 600 °C and 337 MPa, within the α-quartz stability field. Inclusions are re-equilibrated at the same experimental conditions within a pure D₂O fluid environment. Consequently, a gradient in volatile fugacities is the only driving force for diffusion, in the absence of pressure gradients and deformation processes. Up to 100 individual inclusions are analyzed in each experiment before and after re-equilibration by microscopic investigation, microthermometry, and Raman spectroscopy. Changes in fluid inclusion composition are obtained from the ice-melting temperatures, and density changes are obtained from total homogenization temperatures. After 1-day re-equilibration, inclusions already contain up to 11 mol % D₂O. A maximum concentration of 63 mol % D₂O is obtained after 40-day re-equilibration. D₂O concentration profiles in quartz are determined from the concentration in inclusions as a function of their distance to the quartz surface. These profiles illustrate that deep inclusions contain less D₂O than shallow inclusions. At equal depths, a variety of D₂O concentration is observed as a function of fluid inclusion size: Small inclusions are stronger effected compared with large inclusions. A series of 19-day re-equilibration experiments are performed at 300, 400, 500, and 600 °C (at 337 MPa), at the same conditions as the original synthesis. The threshold temperature of diffusion is estimated around 450 °C at 337 MPa, because D₂O is not detected in inclusions from re-equilibration experiments at 300 and 400 °C, whereas maximally 26 mol % D₂O is detected at 500 °C. Our study indicates that the isotopic composition of natural fluid inclusions may be easily modified by re-equilibration processes, according to the experimental conditions at 600 °C and 337 MPa.     

Fluid Inclusion and Carbon-Oxygen Isotope Studies of the Hujiayu Cu Deposit, Zhongtiao Mountains, China: Implications for Syn-metamorphic Copper Remobilization

The Hujiayu Cu deposit,representative of the "HuBi-type" Cu deposits in the Zhongtiao Mountains district in the southern edge of the North China Craton,is primarily hosted in graphitebearing schists and carbonate rocks.The ore minerals comprise mainly chalcopyrite,with minor sphalerite,siegenite[(Co,Ni)_3S_4],and clausthalite[Pb(S,Se)].The gangue minerals are mainly quartz and dolomite,with minor albite.Four fluid inclusion types were recognized in the chalcopyrite-pyrite-dolomite-quartz veins,including CO_2-rich inclusions(type Ⅰ),low-salinity,liquid-dominated,biphase aqueous inclusions(type Ⅱ),solid-bearing aqueous inclusions(type Ⅲ),and solid-bearing aqueous-carbonic inclusions(type Ⅳ).Type I inclusion can be further divided into two sub-types,i.e.,monophase CO_2 inclusions(type Ⅰa) and biphase CO_2-rich inclusions(with a visible aqueous phase),and type Ⅲ inclusion is divided into a subtype with a halite daughter mineral(type Ⅲa) and a subtype with multiple solids(type Ⅲb).Various fluid inclusion assemblages(FIAs) were identified through petrographic observations,and were classified into four groups.The group-1 FIA,consisting of monophase CO_2 inclusions(type Ⅰa),homogenized into the liquid phase in a large range of temperatures from-1 to 28℃,suggesting post-entrapment modification.The group-2 FIA consists of type Ⅰb,Ⅲb and Ⅳ inclusions,and is interpreted to reflect fluid immiscibility.The group-3 FIA comprises type Ⅱ and Ⅲa inclusions,and the group-4FIA consists of type Ⅱ inclusions with consistent phase ratios.The group-1 and group-2 FIAs are interpreted to be entrapped during mineralization,whereas group-3 and group-4 FIAs probably represent the post-mineralization fluids.The solid CO_2 melting temperatures range from-60.6 to56.6℃ and from-66.0 to-63.4℃ for type Ⅰa and type Ⅳ inclusions,respectively.The homogenization temperatures for type Ⅱ inclusions range from 132 to 170℃ for group-3 FIAs and115 to 219℃ for group-4 FIAs.The halite melting temperatures range from 530 to 562℃ for typeⅢ b and Ⅳ inclusions,whereas those for type Ⅲa inclusions range from 198 to 398℃.Laser Raman and SEM-EDS results show that the gas species in fluid inclusions are mainly CO_2 with minor CH_4,and the solids are dominated by calcite and halite.The calcite in the hosting marble and dolomite in the hydrothermal veins have δ~(13)C_(V-pdb) values of-0.2 to 1.2‰ and-1.2 to-6.3‰,and δ~(18)O_(v-smow) values of 14.0 to 20.8 ‰ and 13.2 to 14.3‰,respectively.The fluid inclusion and carbon-oxygen isotope data suggest that the ore-forming fluids were probably derived from metamorphic fluids,which had reacted with organic matter in sedimentary rocks or graphite and undergone phase separation at 1.4-1.8 kbar and 230-240℃,after peak metamorphism.It is proposed that the Hujiayu Cu deposit consists of two mineralization stages.The early stage mineralization,characterized by disseminated and veinlet copper sulfides,probably took place in an environment similar to sediment-hosted stratiform copper mineralization.Ore minerals formed in this precursor mineralization stage were remobilized and enriched in the late metamorphic hydrothermal stage,leading to the formation of thick quartz-dolomite-sulfides veins.     

Juvenile CO2 in enderbites of Tromøy near Arendal, southern Norway: a fluid inclusion and stable isotope study

The enderbites from Tromøy in the central, granulite facies part of the Proterozoic Bamble sector of southern Norway contain dominantly CO₂ and N₂ fluid inclusions. CO₂ from fluid inclusions in quartz segregations in enderbites was extracted by mechanical (crushing) and thermal decrepitation and the δ¹³C measured. Measurement was also made on samples washed in 10% HCl, oxidized with CuO at high temperatures, and step-wise extracted with progressive heating. Results between the different techniques are systematic. The main results show δ¹³C of -4.5±1.5% for crushing and -7±2% for thermal decrepitation. δ¹³C is about constant for CO₂ extracted at different temperatures and points to a homogeneous isotopic composition. Due to the presence of carbonate particles and/or induced contaminations for the extraction by thermal decrepitation, the results for the crushing experiments are assumed the most reliable for fluid-inclusion CO₂. Very low values of δ¹³C have not been found in enderbite samples and δ¹³C combined with δ¹⁸O of the host quartzes (8-11%) indicates juvenile values. In addition, the fluid inclusions were examined by microthermometry and Raman analysis and host quartz by acoustic emission and cathodoluminescence. CO₂ fluid inclusions have varying densities with a frequency maximum of 0.92 g cm^-3 and generally do not concur with trapping densities at granulite conditions. Textures show that CO₂ must have been trapped in fluid inclusions in one early event, but transformed to different extents during late isothermal uplift without important fractionation of isotope compositions. The present data support a model of intrusion and crystallization of a CO₂-rich enderbitic magma at granuiite conditions.     

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.     

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.