The composition and role of the fluid in migmatites: a fluid inclusion study of the Front Range rocks

Monophase negative-crystal shaped CO₂ inclusions occurring isolated, in small clusters, or in well-healed intragranular fractures are common in the leucosome quartz of the 1700m.y.-old migmatites from the east-central Colorado Front Range. They are, however, quite rare in the mafic selvage and paleosome (host rock) quartz. The mode of occurrence suggests that these are the earliest inclusions to form. In addition to the difference in abundance of the inclusions, there is a difference in CO₂-density distribution between migmatitic zones. The temperatures of homogenization for the leucosome inclusions range and +l°C from –67° C to +20° C with two maxima (at –21° C) while those for the paleosome and selvage inclusions are –37° C to +20° C with a single maximum at + 5° C. These differences between the migmatitic zones which occur on the scale of a few centimeters suggest that the formation of these inclusions was related to the migmatization process. The densities corresponding to the Th maxima are appropriate for the P-T conditions for migmatization estimated from the mineral geobarometer/geothermometer. These inclusions must contain nearly pure CO₂, as their final melting temperatures (–56.5° to –57.2° C) are very close to that of the triple point of CO₂. Their composition also was confirmed by Raman spectroscopic analyses.It has been proposed by other workers that CO₂ fluid in the inclusions could form from an H₂O-CO₂ fluid when H₂O is partitioned into the silicate melt. Such partitioning should result in some early H₂O-rich inclusions: H₂O must be released as the melt crystallizes. As found in migmatites from other areas, most aqueous inclusions in the Front Range rocks are obviously much younger than the early CO₂ ones. However, early H₂O-rich fluid may still be preserved, at least in three ways: (A) in rare, isolated or clustered inclusions within quartz inclusions in feldspar; (B) as inclusions in microcline porphyroblasts; (C) in hydrous alteration products of feldspar. (A) contain dilute fluids, 1 to 6 wt% NaCl equivalent. The densities of (A) as well as those of the early CO₂ inclusions found in the quartz inclusions in feldspar are appropriate for the range of P — T conditions estimated for migmatization. These early inclusions must have been preserved because of protected environment. Inclusions (B), found to contain H₂O (and possibly CO₂) by infrared analyses, must be early because they are absent from recrystallized grains. (B) and (C) are much more common in the leucosome than in the other zones suggesting that they are related to migmatization process. The concentration of early CO₂ inclusions in the leucosome is consistent with the model of migmatization in which fluid concentration in the leucosome was a cause of melting.     

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 inclusions as petrogenetic indicators in granulite xenoliths,Pali-Aike volcanic field,Chile

Granulite xenoliths within alkali olivine basalts of the Pali-Aike volcanic field, southern Chile, contain the mineral assemblage orthopyroxene + clinopyroxene + plagioclase + olivine + green spinel. These granulites are thought to be accidental inclusions of the lower crust incorporated in the mantle-derived basalt during its rise to the surface. Symplectic intergrowths of pyroxene and spinel developed between olivine and plagioclase imply that the reaction olivine+plagioclase = Al-orthopyroxene + Al-clinopyroxene + spinel (1) occurred during subsolidus cooling and recrystallization of a gabbroic protolith of the granulites.Examination of fluid inclusions in the granulites indicates the ubiquitous presence of an essentially pure CO₂ fluid phase. Inclusions of three different parageneses have been recognized: Type I inclusions occur along exsolution lamellae in clinopyroxene and are thought to represent precipitation of structurally-bound C or CO₂ during cooling of the gabbro. These are considered the most primary inclusions present. Type II inclusions occur as evenly distributed clusters not associated with any fractures. These inclusions probably represent entrapment of a free fluid phase during recrystallization of the host grains. IIa inclusions are found in granoblastic grains and have densities of 0.68–0.88 g/cm³. Higher density (=0.90–1.02 g/cm³) IIb inclusions occur only in symplectite phases. Secondary Type III CO₂+glass inclusions with =0.47–0.78 g/cm³ occur along healed fractures where basalt has penetrated the xenoliths. Type III inclusions appear related to exsolution of CO₂ from the host basalt during its ascent to the surface. These data suggest that CO₂ is an important constituent of the lower crust under conditions of granulite facies metamorphism, indicated by Type I and II fluid inclusions, and of the mantle, as indicated by Type III inclusions.Correlation of fluid inclusion densities with P-T conditions calculated from both two-pyroxene geothermometry and reation (1) indicate emplacement of a gabbroic pluton at 1,200–1,300° C, 4–6 kb; cooling was accompanied by a slight increase in pressure due to crustal thickening, and symplectite formation occurred at 850±35° C, 5–7 kb. Capture of the xenoliths by the basalt resulted in heating of the granulites, and CO₂ from the basalt was continuously entrapped by the xenoliths over the range 1,000–1,200° C, 4–6 kb. Examination of fluid inclusions of different generations can thus be used in conjunction with other petrologic data to place tight constraints on the specific P-T path followed by the granulite suite, in addition to indicating the nature of the fluid phase present at depth.     

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.     

An experimental study of phase equilibria in the systems H2O–CO2–CaCl2 and H2O–CO2–NaCl at high pressures and temperatures (500–800?°C, 0.5–0.9?GPa): geological and geophysical applications

Phase equilibria in the ternary systems H₂O–CO₂–NaCl and H₂O–CO₂–CaCl₂ have been determined from the study of synthetic fluid inclusions in quartz at 500 and 800 °C, 0.5 and 0.9 GPa. The crystallographic control on rates of quartz overgrowth on synthetic quartz crystals was exploited to prevent trapping of fluid inclusions prior to attainment of run conditions. Two types of fluid inclusion were found with different density or CO₂ homogenisation temperature (T_h(CO₂)): a CO₂-rich phase with low T_h(CO₂), and a brine with relatively high T_h(CO₂). The density of CO₂ was calibrated using inclusions in the binary system H₂O–CO₂. Mass balance calculations constrain tie lines and the miscibility gap between brines and CO₂-rich fluids in the H₂O–CO₂–NaCl and H₂O–CO₂–CaCl₂ systems at 500 and 800 °C, and 0.5 and 0.9 GPa. The miscibility gap in the CaCl₂ system is larger than in the NaCl system, and solubilities of CO₂ are smaller. CaCl₂ demonstrates a larger salting-out effect than NaCl at the same P–T conditions. In ternary systems, homogeneous fluids are H₂O-rich and of extremely low salinity, but at medium to high concentrations of salts and non-polar gases fluids are unlikely to be homogeneous. The two-phase state of crustal fluids should be common. For low fluid-rock ratios the cation compositions of crustal fluids are buffered by major crustal minerals: feldspars and micas in pelites and granitic rocks, calcite (dolomite) in carbonates, and pyroxenes and amphiboles in metabasites. Fluids in pelitic and granitic rocks are Na-K rich, while for carbonate and metabasic rocks fluids are Ca-Mg-Fe rich. On lithological boundaries between silicate and carbonate rocks, or between pelites and metabasites, diffusive cation exchange of the salt components of the fluid will cause the surfaces of immiscibility to intersect, leading to unmixing in the fluid phase. Dispersion of acoustic energy at critical conditions of the fluid may amplify seismic reflections that result from different fluid densities on lithological boundaries.Editorial responsibility: I. Parsons     

Retrograde evolution of quartz segregations from the Dos Picos shear zone in the Nevado-Filabride Complex (Betic chains,Spain). Evidence from fluid inclusions and quartz c-axis fabrics

Synkinematic quartz veins are ubiquitous in the shear zone separating the Veleta unit from the Calar Alto unit in the internal part of the Betic Cordilleras. They have been studied with respect to quartz c-axis fabrics, microstructures and fluid inclusions. Veins were probably generated during syn-metamorphic stacking of the units at P = 500 – 600 MPa and T = 400 – 500°C. Quartz displays two groups of microstructures in the shear zone: (1) older coarse-grained mosaics (CGM) resulting from exaggerated grain growth; and (2) younger fine-grained mosaics (FGM) developed at the expense of the former. The fine-grained mosaics show polygonal granoblastic and elongate mosaic microstructures in general, with ribbon microstructures often found near the boundary of the units. Fluids contained in secondary inclusions vary from high salinity brines to different types of CO₂—brine mixtures and low density CO₂ fluids. Differences in composition and P-T trapping conditions are indicated for the different types of inclusions. Some fluid inclusions are older than the FGM, whereas others are younger, thus constraining the P- T conditions at which the two microstructural events took place. Fluid inclusion evidence suggests conditions of P_fluid > 170 MPa and T 370–430°C for the CGM and P_fluid 20–80 MPa and T > 340°C for the FGM.The quartz c-axis fabrics dealt with here correspond to the second recrystallization event, as little evidence of older fabrics is preserved in the shear zone. C-axis patterns vary across the shear zone from slightly asymmetrical type I crossed girdles in the hanging wall and footwall to more asymmetrical crossed girdles at the boundary of the units. This indicates a correlative increase in the magnitude of the heterogeneous shear strain in the same direction. Most of the deformation is concentrated at the top of the Veleta unit. The sense of movement is top to the west, in agreement with other kinematic markers.The quartz c-axis fabrics resulted from dynamic recrystallization during simple shear. The retrograde P-T path inferred from fluid inclusion analysis, along with other geological and geochronological evidence, indicates that this deformation is coeval with a reduction in the crustal overburden.Geochronological and stratigraphic data show that the proposed Dos Picos extensional detachment, separating the Calar Alto and Veleta units, took place during the early Miocene, synchronous with the intense thinning of the Nevado-Filábride Complex and of the whole continental crust underlying the Alborán Basin.     

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

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

Fluid inclusion evidence for an anticlockwise metamorphic P-T path in central Massachusetts

Acadian (Late Silurian to Early Devonian) metamorphism in the Central Maine Terrane (CMT) in central Massachusetts is characterized by an early low-P, high-T (Buchan-type) metamorphism followed by thickening at high temperature (>650d? C) and then by cooling to 100-200d? C below peak recorded temperatures before eventual unroofing. Mineralogical and textural evidence for this path includes sillimanite pseudomorphs after early andalusite, abundant cordierite in pelitic lithologies, replacement of low-P cordierite-bearing assemblages by high-P garnet-bearing assemblages, and recrystallization of mylonites associated with late shear zones to form lower-T and higher-P assemblages. Peak conditions in the highest grade rocks were 685-780d? C and 5-6 kbar; the cooling path passed through 550d? C at about 6.5 kbar. The well-constrained P-T path documented from geological and mineralogical evidence for the CMT offers an unusual opportunity to examine characteristics of fluid inclusions that have experienced a long-lived metamorphic event spanning a broad range of P-T conditions. Fluid inclusion data from the CMT document a range of fluid compositions (CO₂-rich, mixed CO₂-N₂-rich, N₂-rich and H₂O-rich) and densities during metamorphism. Densities of CO₂ fluid inclusions range from 0.20 to 1.03 g cm^-3. Medium-density CO₂ fluid inclusions are contained in quartz inclusions within garnets in partial melt leucosomes, and in quartz grains within migmatites. Fluid inclusions within the quartz inclusions indicate trapping conditions of 650-700d? C at pressures below 5 kbar. Other CO₂ fluid inclusions from matrix quartz yield isochores which pass through 700d? C and 5.2 kbar. The highest density inclusions associated with rocks containing the late high-P assemblages have isochores which pass below the estimated P-T conditions for recrystallization of the mylonite. Fluid inclusion evidence suggests an early low-P heating event, followed by thickening at high temperature, and then by nearly isobaric cooling to about 500d? C with later decompression. This interpretation is also consistent with previously published petrological models and supports an anticlockwise P-T path for the CMT of south-central Massachusetts.     

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.     

A boundary layer-induced immiscibility in naturally re-equilibrated H2O-CO2-NaCl inclusions from metamorphic quartz (Western Carpathians,Czechoslovakia)

Naturally re-equilibrated fluid inclusions have been found in quartz crystals from alpine fissures of the Western Carpathians. Re-equilibration textures, such as planar arrangement of the decrepitation clusters as well as the quartz c- and a-axis oriented fracturing indicate explosion of fluid inclusions. The extent of fracturing, which is dependent on inclusion diameters, suggests inclusion fluid overpressures between 0.6–1.9 kb. Microthermometry data are controversial with the textures because of indicating roughly fixed initial fluid composition and density during re-equilibration, although inclusion volumes have been sometimes substantially reduced by crystallization of newly-formed quartz. It is concluded that fluid loss from re-equilibrated inclusions must have been compensated for by replacing equivalent quartz volume from cracks into parent inclusion. Such a mechanism has operated in a closed system and the re-equilibration related cracks have not been connected with mineral surface. The compositional and density differences between aqueous inclusions in decrepitation clusters and CO₂-rich parent inclusions cannot be interpreted in terms of classical fluid immiscibility. Moreover, monophase liquid-filled aqueous inclusions and coexisting monophase CO₂ vapour-filled inclusions in the decrepitation clusters are thermodynamically unacceptable under equilibrium metamorphic conditions. The effect of disjoining pressure resulting from structural and electrostatic forces in very thin fractures is suspected to have caused density and compositional inconsistencies between parent and cluster inclusions, as well as the unusual appearance of cluster inclusions. In high-grade metamorphic conditions, the re-equilibration probably leads to boundary layer-induced immiscibility of homogeneous H₂O–CO₂–NaCl fluids and to formation of compositionally contrasting CO₂-rich and aqueous inclusions.     

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 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.     

Mobility of metamorphic fluids inferred from infrared microspectroscopy on natural fluid inclusions: the example of Tinos Island,Greece

OH structure of metamorphic fluids has been studied by high temperature infrared (IR) microspectroscopy on natural fluid inclusions contained in quartz veins, over the temperature range 25–370 °C. Blueschist-facies veins from Tinos island core complex (Cyclades, Greece) display H₂O–NaCl–CaCl₂–CO₂ inclusions whereas greenschist-facies veins contain H₂O–NaCl ± CO₂ inclusions. From 25 to 370 °C, peak positions of OH stretching IR absorption bands increase quasi-linearly with slopes of 0.25 and 0.50 cm^–1 °C^–1 for inclusions trapped under blueschist and greenschist conditions, respectively. Extrapolation to 400 °C yield peak positions of 3,475 cm^–1 for blueschist inclusions and 3,585 cm^–1 for greenschist inclusions. Because the smaller wave number indicates the shorter hydrogen-bond distance between water molecules, fluids involved in the greenschist event have a loose structure compared with blueschist fluids. We suggest that these properties might correspond to a low wetting angle of fluids. This would explain the high mobility of aqueous fluids suggested by structural observation and stable isotope analysis.Editorial responsibility: J. Hoefs     

High-precision analysis of carbon isotopic composition for individual CO2 inclusions via Raman spectroscopy to reveal the multiple-stages evolution of CO2- bearing fluids and melts

The carbon isotopic composition of CO₂ inclusions trapped in minerals reflects the origin and evolution of CO₂-bearing fluids and melts, and records the multiple-stages carbon geodynamic cycle, as CO₂ took part in various geological processes widely. However, the practical method for determination isotope composition of individual CO₂ inclusion is still lacking. Developing a microanalytical technique with spatial resolution in micrometers to precisely determinate the δ¹³C value of individual CO₂ inclusion, will make it possible to analyze a tiny portion of a zoning mineral crystal, distinguish the differences in micro-scale, and possible to find many useful information that could not be obtained with the bulk extraction and analysis techniques. In this study, we systematically collected Raman spectra of CO₂ standards with different δ¹³C values (?34.9 ‰ to 3.58 ‰) at 32.0 °C and from ～7.0 MPa to 120.0 MPa, and developed a new procedure to precisely determinate the δ¹³C value of individual CO₂ inclusion. We investigated the relationship among the Raman peak intensity ratio, δ¹³C value, and CO₂ density, and established a calibration model with high accuracy (0.5 ‰?1.5 ‰), sufficient for geological application to distinguish different source of CO₂ with varying δ¹³CO₂. As a demonstration, we measured the δ¹³C values and the density of CO₂ inclusions in the growth zones of alkali basalt-hosted corundum megacrysts from Changle, Shandong Province. We found the significant differences of density and δ¹³C between the CO₂ inclusions in the core of corundum and those inclusions in the outer growth zones, the δ¹³C value decreases from core to rim with decreasing density: δ¹³C values are from ?7.5 ‰ to ?9.2 ‰ for the inclusions in the core, indicating the corundum core was crystallized from mantle-derived magmas; from ?13.5 ‰ to ?18.5 ‰ for CO₂ inclusions in zone 1 and from ?16.5 ‰ to –22.0 ‰ for inclusions in zone 2, indicating the outer zones of corundum grew in a low δ¹³C value environment, resulted from an infilling of low δ¹³C value fluid and/or degassing of the ascending basaltic magma.     

Fluid and silicate glass inclusions in ultramafic and mafic xenoliths from Hierro,Canary Islands: implications for mantle metasomatism

Fluid and solid inclusions have been studied in selected samples from a series of spinel-bearing Crdiopside-and Al-augite-series ultramafic (harzburgites, lherzolites, and olivine-clinopyroxene-rich rocks), and gabbroic xenoliths from Hierro, Canary Islands. In these samples several generations of fluid inclusions and ultramafic-and mafic-glass inclusions may be texturally related to different stages of crystal growth. The fluid inclusions consist of pure, or almost pure, CO₂. The solid inclusions in the ultramafic xenoliths comprise early inclusions of devitrified ultramafic glass, sulphide inclusions, as well as polyphase inclusions (spinel+clinopyroxene±glass±other silicates) believed to have formed from trapped basaltic melts. Vitreous basaltic glass±CO₂±sulphide±silicates are common as secondary inclusions in the ultramafic xenoliths, and as primary inclusions in the gabbroic xenoliths. Microthermometry gives minimum trapping temperatures of 1110° C for the early ultramafic-and mafic-glass inclusions, and a maximum of 1260–1280° C for late inclusions of host basaltic glass. In most samples the CO₂ inclusions show a wide range in homogenization temperatures (-40 to +31° C) as a result of decrepitation during ascent. The lowest homogenization temperatures of about-40° C, recorded in some of the smallest CO₂ inclusions, indicate a minimum depth of origin of 35 km (12 kbar) for both the Cr-diopside-and Al-augite-series xenoliths. The gabbroic xenoliths originate from a former magma chamber at a depth of 6–12 km.Contribution no. 100 of the Norwegian programme of the International Lithosphere Project     

Origin of CO2-rich fluid inclusions in leucosomes from the Skagit migmatites, North Cascades, Washington, USA

CO₂–CH₄ fluid inclusions are present in anatectic layer-parallel leucosomes from graphite-bearing metasedimentary rocks in the Skagit migmatite complex, North Cascades, Washington. Petrological evidence and additional fluid inclusion observations indicate, however, that the Skagit Gneiss was infiltrated by a water-rich fluid during high-temperature metamorphism and migmatization. CO₂-rich fluid inclusions have not been observed in Skagit metasedimentary mesosomes or melanosomes, meta-igneous migmatites, or unmigmatized rocks, and are absent from subsolidus leucosomes in metasedimentary migmatites. The observation that CO₂-rich inclusions are present only in leucosomes interpreted to be anatectic based on independent mineralogical and chemical criteria suggests that their formation is related to migmatization by partial melting. Although some post-entrapment modification of fluid inclusion composition may have occurred during decompression and deformation, the generation of the CO₂-rich fluid is attributed to water-saturated partial melting of graphitic metasedimentary rocks by a reaction such as biotite + plagioclase + quartz + graphite ± Al₂SiO₅+ water-rich fluid = garnet + melt + CO₂–CH₄. The presence of CO₂-rich fluid inclusions in leucosomes may therefore be an indication that these leucosomes formed by anatexis. Based on the inferences that (1) an influx of fluid triggered partial melting, and (2) some episodes of fluid inclusion trapping are related to migmatization by anatexis, it is concluded that a free fluid was present at some time during high-temperature metamorphism. The infiltrating fluid was a water-rich fluid that may have been derived from nearby crystallizing plutons. Because partial melting took place at pressures of at least 5 kbar, abundant free fluid may have been present in the crust during orogenesis at depths of at least 15 km.     

Fluid inclusions in granulite-facies metapelites of the Hercynian ancient lower crust of the Serre,Calabria, Southern Italy

Investigations of fluid inclusions in granulitefacies metapelites of southern Calabria enable characterization of the fluid composition of these lower crustal rocks, and constrain the petrologically deduced retrograde P-T path characterized by isothermal uplift prior to isobaric cooling in middle crustal levels. Fluid inclusions in cordierite, garnet and sillimanite have a CO₂-rich composition. Inclusions in cordierite rarely contain minor amounts of N₂ and H₂O, and in garnets some CO₂–CH₄–N₂ inclusions have been analyzed by Raman microprobe. Quartz reveals the most complex fluid melusion compositions (1) CO₂-rich, (2) CO₂–CH₄–N₂, (3) CH₄–N₂, (4) H₂O–MgCl₂–CaCl₂–NaCl, (5) H₂O–NaCl and (6) H₂O–CO₂. The earliest fluid inclusions after peak metamorphism are rich in CO₂ with minor amounts of N₂ and H₂O. An early CO₂–(H₂O–N₂) fluid composition has been confirmed by detection of CO₂, H₂O and N₂ in the channels of the cordierite structure. Most of the early CO₂-rich fluid inclusions were modified during the uplift from the lower to the middle crustal level, resulting in a density decrease with CO₂ still dominant. The subsequent isobaric cooling led to further modifications of the fluid inclusions. High-density inclusions around implosion textures or scattered amongst lower-density ones must have formed during this cooling episode. Aqueous inclusions in quartz are mostly formed late and are consistent with trapping during retrograde rehydration.This project has been supported by the DFG as contribution to the special program Continental Lower Crust     

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.     

Multi-stage evolution of the picritic Mælifell rocks,SW Iceland: constraints from mineralogy and inclusions of glass and fluid in olivine

The picritic Mælifell pillow lava series contains olivine macrocrysts (Fo 83.0–91.7) and microphenocrysts (Fo 86.8–88.5), resorbed Cr–Al endiopside, ± plagioclase, and microphenocrysts of Cr-spinel. The most primitive olivine cores (Fo 90–91.7) are probably derived from a peridotitic mantle. Gabbroic adcumulus xenoliths in the lavas contain plagioclase, Cr–Al endiopside and olivine (Fo 85.5–87.5) which overlap compositionally with lava minerals, ± Cr-spinel. This suggests that all pyroxene and much of the olivine ± feldspar in the lavas are xenocrysts. Olivines from the pillow lavas and from the gabbroic xenoliths contain inclusions of Cr-spinel, silicate glass and pure or nearly pure CO₂. Early (type 1) silicate melt inclusions which occur in lava-olivine only, have crystalized 0.1 to 4 vol.% daughter spinel and unknown amounts of olivine during pre-eruptive cooling. Later (type 2) glass inclusions in olivine from the lavas do not contain daughter minerals; similar type 2 inclusions also occur in the xenoliths. High-temperature microthermometry at buffered oxygen fugacity (f _{O 2}) gives a plagioclaseout temperature of about 1230°C for both types of silicate melt inclusions; this was interpreted as the liquidus temperature for type 2 inclusions. Molar volumes of undisturbed CO₂ inclusions in olivine from both lavas and xenoliths correspond to a depth of trapping of 7–10 km (2.2–3.0 kbar) at 1230°C. This is interpreted as a minimum depth to a partially molten layer near the crust/mantle boundary in the rift zone. The xenoliths are thus probably derived from a layered olivine-gabbro complex similar to those occurring in ophiolite complexes.     

Fluid inclusion study of Xihuashan tungsten deposit in the southern Jiangxi province,China

The Xihuashan tungsten deposit is closely related to a small highly evolved granitic intrusion. The fluid phases associated with the wolframite-bearing quartz veins have been investigated using microthermometry and the Raman microprobe; they are highly variable in density and composition. The earlier fluids are low-density and low-salinity CO₂-bearing aqueous solutions circulating at temperatures up to 420 °C, and low-salinity (2–3 equiv. wt% NaCl) aqueous solutions without traces of CO₂ circulating at high temperatures 280°–400 °C) involved in a specific hydrothermal fracturing event; limited unmixing occurs at 380 °C and 200–100 bar in response to a sudden pressure drop. The second types of fluids related to deposition of idiomorphic drusy quartz are typical CO₂-bearing aqueous solutions with low salinity (2.5 equiv. wt% NaCl) homogenizing at low to moderate temperatures (180°–340 °C). The late fluids characterize the sulfide deposition stage; they are aqueous fluids with variable salinities homogenizing in the liquid phase between 100° and 275 °C. The Xihuashan hydrothermal evolution resulted from a discontinuous sequence of specific events occurring between 420° and 150 °C and during a continuous hydrothermal evolution of the system during cooling. The role played by the CO₂-rich fluids in the transport and deposition of tungsten in the hydrothermal environment is discussed.