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.     

Fluid inclusions in high-grade gneisses of the Kapuskasing structural zone,Ontario: metamorphic fluids and uplift/erosion path

Fluid inclusions in quartz grains from five samples of high-grade rocks (two paragneisses, an amphibolite, a mafic gneiss and a tonalite dike) from the 2.7 Ga Kapuskasing structural zone (KSZ), Ontario, were examined with petrographic, microthermometric and laser Raman techniques. Three types of fluid inclusions were observed: CO₂-rich, H₂O-rich and mixed CO₂-H₂O. CO₂-rich fluid inclusions are pseudosecondary or secondary in nature and are generally pure CO₂; a few contain varying amounts of CH₄·H₂O-rich fluid inclusions are secondary in nature, contain variable amounts of dissolved salts, and generally contain daughter crystals. Mixed CO₂-H₂O fluid inclusions occur where trails of H₂O-rich inclusions intersect trails of CO₂-rich inclusions. Isochores for high density (p=1.03 g/cm³) pseudosecondary, pure CO₂ inclusions intersect the lower pressure portion of the estimated P-T field for high-grade metamorphism, implying that pure CO₂ was the peak metamorphic fluid. The variable CH₄ content of CO₂ inclusions within graphite-bearing samples suggests that CH₄ was introduced locally after the formation of the CO₂ inclusions; however the origin of the CH₄ remains problematic. An aqueous fluid clearly penetrated the gneisses after the peak metamorphism (during uplift/erosion), forming secondary inclusions and contributing to the minor retrogressive hydration observed in these rocks. The presence of the pseudosecondary, high-density CO₂ inclusions in quartz crystals in the KSZ rocks constrains the uplift/ erosion path for the KSZ to one of simultaneous decrease in pressure and temperature.     

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.     

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.     

The origin and significance of non-aqueous CO2 fluid inclusions in the auriferous veins of Bin Yauri,northwestern Nigeria

Non-aqueous CO₂ and CO₂-rich fluid inclusions are found in the vein quartz hosting mesothermal gold-sulphide mineralization at Bin Yauri, northwestern Nigeria. Although mineralizing fluids responsible for gold mineralization are thought to be CO₂-rich, the occurrence of predominantly pure to nearly pure CO₂ inclusions is nevertheless unusual for a hydrothermal fluid system. Many studies of similar CO₂-rich fluid inclusions, mainly in metamorphic rocks, proposed preferential loss (leakage) of H₂O from H₂O-CO₂ inclusions after entrapment. In this study however, it is proposed that phase separation (fluid immiscibility) of low salinity CO₂-rich hydrothermal fluids during deposition of the gold mineralization led to the loss of the H₂O phase and selective entrapment of the CO₂. The loss of H₂O to the wallrocks resulted in increasing oxidizing effects. There is evidence to suggest that the original CO₂-rich fluid was intrinsically oxidized, or perhaps in equilibrium with oxidizing conditions in the source rocks. The source of the implicated fluid is thought to be subducted metasediments, subjected to dehydration and devolatilization reactions along a transcurrent Anka fault/shear system, which has been described as a Pan-African (450–750 Ma) crustal suture.     

Pan-African high-grade metamorphism of southern Sinai,Egypt, fluid inclusion evidence

Fluid inclusions in the leucosomes of Wadi Feiran migmatites showed that CO ₂ , H₂O and (H₂O-CO₂) fluids were likely to have been present when partial melting began in these rocks. Low salinity, aqueous fluid, to a lesser extent, CO₂-rich fluids are the most abundant fluids. The present study suggests that high-density CO₂ inclusions were formed at the earliest stage, while H₂O inclusions were formed at the late stage. In an intermediate stage, low-density CO₂ and H₂O, CO₂ inclusions were formed. At the early stage of uplift and during melt crystallization, the CO₂-bearing vapour was trapped at grain boundaries. At the late stage of uplift, H₂O released at the time of crystallization of the melt was trapped as inclusions.     

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.     

http://www.sciencedirect.com/science/article/pii/S1674987114000218

Fluid infiltration into retrograde granulites of the Southern Marginal Zone(Limpopo high grade terrain)is exemplified by hydration reactions.shear zone hosted metasomatism,and lode gold mineralisation.Hydration reactions include the breakdown of cordierite and orthopyroxene to gedrite kyanite,and anthophyllite,respectively.Metamorphic petrology,fluid inclusions,and field data indicate that a low H_2O-activity carbon-saturated CO_2-rich and a saline aqueous fluid infiltrated the Southern Marginal Zone during exhumation.The formation of anthophyllite after orthopyroxene eslablished a regional retrograde anthophyllite-in isograd and occurred at P-T conditions of- 6 kbar and 610 C,which fixes the minimum mole fraction of II.0 in the CO_2-rich fluid phase at- 0.1.The maximum H_2O mole fraction is hxed by the lower temperature limit(~800℃) for partial melting at ~0.3.C-O-H fluid calculations show that the CO_2-rich fluid had an oxygen fugacity that was 0.6 log10 units higher than that of the fayalite-magnetitequartz buffer and that the CO_2/(CO_2+CH_4) mole ratio of this fluid was 1.The presence of dominantly relatively low density CO_2-rich fluid inclusions in the hydrated granulites indicates that the fluid pressure was less than the lithostatic pressure.This can be explained by strike slip faulting and/or an increase of the rock permeability caused by hydration reactions.     

Reaction textures and fluid behaviour in very high pressure calc-silicate rocks of the Münchberg gneiss complex, Bavaria, Germany

Calc-silicate rocks occur as elliptical bands and boudins intimately interlayered with eclogites and high-pressure gneisses in the Münchberg gneiss complex of NE Bavaria. Core assemblages of the boudins consist of grossular-rich garnet, diopside, quartz, zoisite, clinozoisite, calcite, rutile and titanite. The polygonal granoblastic texture commonly displays mineral relics and reaction textures such as post kinematic grossular-rich garnet coronas. Reactions between these mineral phases have been modelled in the CaO-Al₂O₃-SiO₂-CO₂-H₂O system with an internally consistent thermodynamic data base. High-pressure metamorphism in the calc-silicate rocks has been estimated at a minimum pressure of 31 kbar at a temperature of 630d? C with X_H2, O ≥ 0.03. Small volumes of a CO₂-N₂-rich fluid whose composition was buffered on a local scale were present at peak-metamorphic conditions. The P-T conditions for the onset of the amphibolite facies overprint are about 10 kbar at the same temperature. X_Co2 of the H₂O-rich fluid phase is regarded to have been <0.03 during amphibolite facies conditions. These P-T estimates are interpreted as representing different stages of recrystallization during isothermal decompression. The presence of multiple generations of mineral phases and the preservation of very high-pressure relics in single thin sections preclude pervasive post-peak metamorphic fluid flow as a cause of a re-equilibration within the calc-silicates. The preservation of eclogite facies, very high-pressure relics as well as amphibolite facies reactions textures in the presence of a fluid phase is in agreement with fast, tectonically driven unroofing of these rocks.     

Fluid and gas migration in the North German Basin: fluid inclusion and stable isotope constraints

Fluid inclusions have been studied in minerals infilling fissures (quartz, calcite, fluorite, anhydrite) hosted by Carboniferous and Permian strata from wells in the central and eastern part of the North German Basin in order to decipher the fluid and gas migration related to basin tectonics. The microthermometric data and the results of laser Raman spectroscopy reveal compelling evidence for multiple events of fluid migration. The fluid systems evolved from a H₂O–NaCl±KCl type during early stage of basin subsidence to a H₂O–NaCl–CaCl₂ type during further burial. Locally, fluid inclusions are enriched in K, Cs, Li, B, Rb and other cations indicating intensive fluid–rock interaction of the saline brines with Lower Permian volcanic rocks or sediments. Fluid migration through Carboniferous sediments was often accompanied by the migration of gases. Aqueous fluid inclusions in quartz from fissures in Carboniferous sedimentary rocks are commonly associated with co-genetically trapped CH₄–CO₂ inclusions. P–T conditions estimated, via isochore construction, yield pressure conditions between 620 and 1,650 bar and temperatures between 170 and 300°C during fluid entrapment. The migration of CH₄-rich gases within the Carboniferous rocks can be related to the main stage of basin subsidence and stages of basin uplift. A different situation is recorded in fluid inclusions in fissure minerals hosted by Permian sandstones and carbonates: aqueous fluid inclusions in calcite, quartz, fluorite and anhydrite are always H₂O–NaCl–CaCl₂-rich and show homogenization temperatures between 120 and 180°C. Co-genetically trapped gas inclusions are generally less frequent. When present, they show variable N₂–CH₄ compositions but contain no CO₂. P–T reconstructions indicate low-pressure conditions during fluid entrapment, always below 500 bar. The entrapment of N₂–CH₄ inclusions seems to be related to phases of tectonic uplift during the Upper Cretaceous. A potential source for nitrogen in the inclusions and reservoirs is C_org-rich Carboniferous shales with high nitrogen content. Intensive interaction of brines with Carboniferous or even older shales is proposed from fluid inclusion data (enrichment in Li, Ba, Pb, Zn, Mg) and sulfur isotopic compositions of abundant anhydrite from fissures. The mainly light δ³⁴S values of the fissure anhydrites suggest that sulfate is either derived through oxidation and re-deposition of biogenic sulfur or through mixing of SO₄²⁻-rich formation waters with variable amounts of dissolved biogenic sulfide. An igneous source for nitrogen seems to be unlikely since these rocks have low total nitrogen content and, furthermore, even extremely altered volcanic rocks from the study area do not show a decrease in total nitrogen content.     

Post-metamorphic CO2-rich fluid inclusions in granulites

In granulite-facies samples from the Adirondack Mountains, NY, estimates of peak-metamorphic CO₂ fugacities based on mineral equilibria are not consistent with estimates based on data for high-density, CO₂-rich fluid inclusions. Of the 21 Adirondack samples investigated for this study, all contain CO₂-rich inclusions. Inclusions occur in quartz, apatite, and garnet. They range in size from 3 to 50 m and are without visible H₂O. In a few of the inclusions, freezing point determinations and preliminary Laser Raman spectroscopy show the presence of small amounts (<3%) of other fluids (N₂ and H₂S). CO₂ liquid-vapor homogenization temperatures are between –46 and +31° C, corresponding to densities between 1.14 and 0.5 gm/cc. Some of these densities are consistent with peak-metamorphic entrapment (1.06 to 1.1 gm/cc).Peak metamorphic fluid compositions in these samples are inferred from fluid-buffering equilibria that restrict the fugacity of CO₂ (f CO₂) directly (i.e., calcite+quartz+wollastonite) or buffer the fugacity of oxygen (f O₂). Assemblages that bufferf O₂ are important because knowledge off O₂ places an upper limit onf CO₂. In 13 of the 21 samples, estimates of peak-metamorphic fluid compositions based on these equilibria show that the mole fraction of CO₂ (XCO₂) in equilibrium with the rock was low, in some cases less than 0.2.The contradiction of mineral equilibria and fluid inclusion data shows that the inclusions record post-metamorphic conditions. At present, there are no criteria to distinguish these primary appearing CO₂-rich inclusions from those found in other granulite-facies terranes. Therefore, inferences of pressure-temperature conditions and peakmetamorphic fluid compositions based on fluid inclusions must be viewed with caution.     

Anatexis and fluid regime of the deep continental crust: New clues from melt and fluid inclusions in metapelitic migmatites from Ivrea Zone (NW Italy)

We investigate the inclusions hosted in peritectic garnet from metapelitic migmatites of the Kinzigite Formation (Ivrea Zone, NW Italy) to evaluate the starting composition of the anatectic melt and fluid regime during anatexis throughout the upper amphibolite facies, transition, and granulite facies zones. Inclusions have negative crystal shapes, sizes from 2 to 10 μm and are regularly distributed in the core of the garnet. Microstructural and micro‐Raman investigations indicate the presence of two types of inclusions: crystallized silicate melt inclusions (i.e., nanogranitoids, NI), and fluid inclusions (FI). Microstructural evidence suggests that FI and NI coexist in the same cluster and are primary (i.e., were trapped simultaneously during garnet growth). FI have similar compositions in the three zones and comprise variable proportions of CO₂, CH₄, and N₂, commonly with siderite, pyrophyllite, and kaolinite, suggesting a COHN composition of the trapped fluid. The mineral assemblage in the NI contains K‐feldspar, plagioclase, quartz, biotite, muscovite, chlorite, graphite and, rarely, calcite. Polymorphs such as kumdykolite, cristobalite, tridymite, and less commonly kokchetavite, were also found. Rehomogenized NI from the different zones show that all the melts are leucogranitic but have slightly different compositions. In samples from the upper amphibolite facies, melts are less mafic (FeO + MgO = 2.0–3.4 wt%), contain 860–1700 ppm CO₂ and reach the highest H₂O contents (6.5–10 wt%). In the transition zone melts have intermediate H₂O (4.8–8.5 wt%), CO₂ (457–1534 ppm) and maficity (FeO + MgO = 2.3–3.9 wt%). In contrast, melts at granulite facies reach highest CaO, FeO + MgO (3.2–4.7 wt%), and CO₂ (up to 2,400 ppm), with H₂O contents comparable (5.4–8.3 wt%) to the other two zones. Our results represent the first clear evidence for carbonic fluid‐present melting in the Ivrea Zone. Anatexis of metapelites occurred through muscovite and biotite breakdown melting in the presence of a COH fluid, in a situation of fluid–melt immiscibility. The fluid is assumed to have been internally derived, produced initially by devolatilization of hydrous silicates in the graphitic protolith, then as a result of oxidation of carbon by consumption of Fe³⁺‐bearing biotite during melting. Variations in the compositions of the melts are interpreted to result from higher T of melting. The H₂O contents of the melts throughout the three zones are higher than usually assumed for initial H₂O contents of anatectic melts. The CO₂ contents are highest at granulite facies, and show that carbon‐contents of crustal magmas are not negligible at high T. The activity of H₂O of the fluid dissolved in granitic melts decreases with increasing metamorphic grade. Carbonic fluid‐present melting of the deep continental crust represents, together with hydrate‐breakdown melting reactions, an important process in the origin of crustal anatectic granitoids.     

Re-equilibration of CO2 fluid inclusions at controlled hydrogen fugacities

Abstract Natural, pure CO₂ inclusions in quartz and olivine (c. Fo₉₀) were exposed to controlled f_H2 conditions at T= 718–728°C and P_total= 2 kbar; their compositions were monitored (before and after exposures) by microsampling Raman spectroscopy (MRS) and microthermometry. In both minerals exposed at the graphite–methane buffer (f_H2= 73 bar), fluid speciations record the diffusion of hydrogen into the inclusions. In quartz, room-temperature products in euhedral isolated (EI type) inclusions are carbonic phases with molar compositions of c. CO₂(60) + CH₄(40) plus graphite (Gr) and H₂O, whereas anhedral inclusions along secondary fractures (AS type) are Gr-free and contain H₂O plus carbonic phases with compositions in the range c. CO₂(60) + CH₄(40) to CO₂(10) + CH₄(90). EI type inclusions in olivine evolved to c. CO₂(90–95) + CH₄(5–10) without Gr, whereas AS type inclusions have a range of compositions from CO₂(90) + CH₄(10) ± Gr to CH₄(50) + H₂(50) ± Gr; neither H₂O nor any hydrous species was detected by optical microscopy or MRS in the olivine-hosted products. Differences in composition between and among the texturally distinct populations of inclusions in both minerals probably arise from variations in initial fluid densities, as all inclusions apparently equilibrated with the ambient f_H2. These relations suggest that compositional variability among inclusions in a given natural sample does not require the entrapment of multiple generations of fluids. In addition, the absence of H₂O in the olivine-hosted inclusions would require the extraction of oxygen from the fluids, in which case re-equilibration mechanisms may be dependent on the composition and structure of the host mineral. Many of the same samples were re-exposed to identical P–T conditions using Ar as the pressure medium, yielding ambient f_H2= 0.06 bar. In most inclusions, the carbonic fluids returned to pure CO₂ and graphite persisted in the products. Reversal of the mechanisms from the prior exposure at f_H2= 73 bar did not occur in any inclusions but the AS types in olivine, in which minor CO₂ was produced at the expense of CH₄ and/or graphite. The observed non-reversibility of previous mechanisms may be attributed to: (1) slower fluid–solid reactions compared to reactions in the homogeneous fluid phase; (2) depressed activities of graphite due to poor ordering; and/or (3) low ambient f_O2 at the conditions of the second run.     

Fluids in granulites of the Southern Marginal Zone of the Limpopo Belt, South Africa

The Southern Marginal Zone of the Limpopo Belt in South Africa is characterised by a granulite and retrograde hydrated granulite terrane. The Southern Marginal Zone is, therefore, perfectly suitable to study fluids during and after granulite facies metamorphism by means of fluid inclusions and equilibrium calculations. Isolated and clustered high-salinity aqueous and CO₂(-CH₄) fluid inclusions within quartz inclusions in garnet in metapelites demonstrate that these immiscible low H₂O activity fluids were present under peak metamorphic conditions (800-850 °C, 7.5-8.5 kbar). The absence of widespread high-temperature metasomatic alteration indicates that the brine fluid was probably only locally present in small quantities. Thermocalc calculations demonstrate that the peak metamorphic mineral assemblage in mafic granulites was in equilibrium with a fluid with a low H₂O activity (0.2-0.3). The absence of water in CO₂-rich fluid inclusions is due to either observation difficulties or selective water leakage. The density of CO₂ inclusions in trails suggests a retrograde P-T path dominated by decompression at T<600 °C. Re-evaluation of previously published data demonstrates that retrograde hydration of the granulites at 600 °C occurred in the presence of H₂O and CO₂-rich fluids under P-T conditions of 5-6 kbar and ~600 °C. The different compositions of the hydrating fluid suggest more than one fluid source.     

High integrated fluid/rock ratios during metamorphism at Naxos: evidence from carbon isotopes of calcite in schists and fluid inclusions

Calcite in schists of the metamorphic complex at Naxos is depleted both in ¹³C and in ¹⁸O with respect to massive marbles. This effect is attributed to isotope exchange with circulating CO₂-rich fluids, which had an >0.5 according to fluid inclusions. The carbon isotopic composition of the calcites is close to equilibrium with fluid inclusion CO₂ at metamorphic temperatures. Mass balance calculations assuming initial ¹³C values of 0 for calcite and –5 for the fluid, give integrated fluid/rock volume ratios between 0.1 and 2.0. Such high fluid/rock ratios are supported by observations on the distribution of CO₂/H₂O ratios of fluid inclusions, carbon isotopic compositions of fluid inclusion CO₂ and oxygen isotope systematics of silicates.     

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     

Ore Genesis and Tectonic Significance of the Xiaojiashan Tungsten Deposit,Eastern Tianshan,Xinjiang, China: Evidence from Geology,Fluid Inclusions,and Stable Isotope Geochemistry

The Xiaojiashan tungsten deposit is located about 200 km northwest of Hami City, the Eastern Tianshan orogenic belt, Xinjiang, northwestern China, and is a quartz vein‐type tungsten deposit. Combined fluid inclusion microthermometry, host rock geochemistry, and H–O isotopic compositions are used to constrain the ore genesis and tectonic setting of the Xiaojiashan tungsten deposit. The orebodies occur in granite intrusions adjacent to the metamorphic crystal tuff, which consists of the second lithological section of the first Sub‐Formation of the Dananhu Formation (D₂d ₁²). Biotite granite is the most widely distributed intrusive bodies in the Xiaojiashan tungsten deposit. Altered diorite and metamorphic crystal tuff are the main surrounding rocks. The granite belongs to peraluminous A‐type granite with high potassic calc‐alkaline series, and all rocks show light Rare Earth Element (REE)‐enriched patterns. The trace element characters suggest that crystallization differentiation might even occur in the diagenetic process. The granite belongs to postcollisional extension granite, and the rocks formed in an extensional tectonic environment, which might result from magma activity in such an extensional tectonic environment. Tungsten‐bearing quartz veins are divided into gray quartz vein and white quartz veins. Based on petrography observation, fluid inclusions in both kinds of vein quartz are mainly aqueous inclusions. Microthermometry shows that gray quartz veins have 143–354°C of T_h, and white quartz veins have 154–312°C of T_h. The laser‐Raman test shows that CO₂ is found in fluid inclusions of the tungsten‐bearing quartz veins. Quadrupole mass spectrometry reveals that fluid inclusions contain major vapor‐phase contents of CO₂, H₂O. Meanwhile, fluid inclusions contain major liquid‐phase contents of Cl^?, Na⁺. It can be speculated that the ore‐forming fluid of the Xiaojiashan tungsten deposit is characterized by an H₂O–CO₂, low salinity, and H₂O–CO₂–NaCl system. The range of hydrogen and oxygen isotope compositions indicated that the ore‐forming fluids of the tungsten deposit were mainly magmatic water. The ore‐forming age of the Xiaojiashan deposit should to be ~227 Ma. During the ore‐forming process, the magmatic water had separated from magmatic intrusions, and the ore‐bearing complex was taken to a portion where tungsten‐bearing ores could be mineralized. The magmatic fluid was mixed by meteoric water in the late stage.     

The P-V̄-T-X-f O2 evolution of H2O-CO2-CH4-bearing fluid in a wolframite vein: Reconstruction from fluid inclusion studies

Aqueous-carbonaceous and later pure aqueous fluid inclusions in quartz from a ferberite (Fe_.95Mn_.05 WO₄) vein within the low-grade metamorphic aureole of the Borne granite (French Massif Central) have been studied by microthermometry and Raman spectrometry. The bulk V?-X properties of the aqueous-carbonaceous inclusions have been derived using the equation of state of Heyenet al. (1982) for the low-temperature CO₂-CH₄ system. A P-T path has been proposed for their trapping using the equations of state of Jacobs and Kerrick (1981a) for the H₂O-CO₂-CH₄ system. Two main episodes were reconstructed for the history of the aqueous-carbonaceous fluid. (1) Primary H₂O-CO₂-CH₄ vapourrich inclusions in quartz indicated the early circulation of a low-density fluid (65 mole% H₂O-34 mole% CO₂-1 mole% CH₄ and traces of N₂: d = 0.35 gcm^?3) at around 550° ± 50°C and 700 ± 100 bar. Fluid cooled approximately isobarically to 450°-400°C and was progressively diluted by H₂O with a concomitant increase in density. The fO₂ of the H₂OCO₂-CH₄ fluid, estimated from the equilibrium CO₂ + 2H₂O CH₄ + 2O₂, first ranged from 10^?22 to 10^?27 bar, close to the Q-F-M buffer. Within analytical errors, these values were consistent with the presence of graphite in equilibrium with the fluid. (2) A drop in PCO₂, and therefore a drop in fO₂, was recorded by the secondary liquid-rich inclusions in quartz. The inclusions, formed at and below 400°C, were composed of H₂O and CH₄ only, and fO₂ at that stage was below that fixed by the graphite-fluid equilibrium. This second episode in the fluid-rock system could be explained by the drop of temperature below the blocking temperature of the graphite-fluid equilibrium. According to this interpretation, the blocking of the graphite-fluid equilibrium occurred at T ≥ 370°C and probably at 400°C on account of the pressure correction. Mass spectrometric data show that ferberite contains H₂O, CO₂ and CH₄ in fluid inclusions, which lie in the gap of the V?-X properties of the aqueouscarbonaceous fluid in quartz. Deposition of ferberite probably occurred at around 400°C, the previously inferred blocking temperature, resulting from either the drop in PCO₂, the drop fO₂ and/or the related pH-increase.It is concluded that the existence of a blocking-temperature for the graphite-fluid chemical equilibrium may be a critical factor for maintaining a stable fluid pressure gradient in geothermal systems occurring under greenschist facies conditions in graphite-bearing rocks.     

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.     

The world-class Natalka gold deposit, northeast Russia: REE patterns, fluid inclusions, stable oxygen isotopes, and formation conditions of ore

REE patterns of hydrothermally altered rocks, fluid inclusions, and stable oxygen isotopes of quartz were studied at the Natalka gold deposit. Metasomatic rocks formed under decompression reveal gradual depletion in LREE and HREE relative to siltstone of the protolith. The HREE patterns of metasomatic rocks formed under decompression are uniform; an insignificant removal of LREE can be noted. The progressive extraction of REE with increasing alteration of rocks could have been due to the effect of magmatogenic or meteoric fluid. Because a Ce anomaly is absent, the participation of oxidized meteoric water was limited. The inverse correlation between the total REE content and the Eu anomaly value in altered rocks indicates a substantial role of magmatogenic fluid. The REE patterns of altered rocks formed under compression show that the role of metamorphic fluid was not great. All metasomatic rocks are enriched in LREE, so that the enrichment of fluid in LREE as well may be suggested. Three fluid compositions were captured as fluid inclusions: (1) H₂O-CO₂-NaCl-MgCl₂ with a salinity of 1.0–4.9 wt % NaCl equiv, (2) CO₂-CH₄, and (3) H₂O-NaCl-MgCl₂ with a salinity of 7.0–5.6 wt % NaCl equiv. Compositions (1) and (2) coexisted in the mineral-forming system at 250–350°C and 1.1–2.4 kbar as products of phase separation under conditions of decreasing P and T. The interaction of this fluid with host rocks resulted in the formation of extensive halos of beresitized rocks with sulfide disseminations. The precipitation of arsenopyrite and pyrite led to the substantial depletion of mineral-forming fluid in H₂S and destabilization of the Au(HS)^2? complex. The fluid with the third composition arose due to the boiling of the H₂O-CO₂-CH₄-NaCl-MgCl₂ liquid and was responsible for metasomatic alteration of host rocks. The late mineral assemblages were deposited from this fluid at the initial stage of ore formation. The high methane concentrations in the ore-forming fluid were likely caused by interaction of hydrothermal ore-bearing solutions with carbonaceous host rocks. The δ¹⁸O values of quartz from quartz-scheelite-pyrite-arsenopyrite and sulfide-sulfosalt mineral assemblages vary from +11.6 to +14.1‰ and +11.2 to +13.5‰, respectively. The parental fluids of the early and late mineral assemblages probably were derived from a magmatic source and were characterized by $ \delta ^{18} O_{H_2 O} REE patterns of hydrothermally altered rocks, fluid inclusions, and stable oxygen isotopes of quartz were studied at the Natalka gold deposit. Metasomatic rocks formed under decompression reveal gradual depletion in LREE and HREE relative to siltstone of the protolith. The HREE patterns of metasomatic rocks formed under decompression are uniform; an insignificant removal of LREE can be noted. The progressive extraction of REE with increasing alteration of rocks could have been due to the effect of magmatogenic or meteoric fluid. Because a Ce anomaly is absent, the participation of oxidized meteoric water was limited. The inverse correlation between the total REE content and the Eu anomaly value in altered rocks indicates a substantial role of magmatogenic fluid. The REE patterns of altered rocks formed under compression show that the role of metamorphic fluid was not great. All metasomatic rocks are enriched in LREE, so that the enrichment of fluid in LREE as well may be suggested. Three fluid compositions were captured as fluid inclusions: (1) H₂O-CO₂-NaCl-MgCl₂ with a salinity of 1.0–4.9 wt % NaCl equiv, (2) CO₂-CH₄, and (3) H₂O-NaCl-MgCl₂ with a salinity of 7.0–5.6 wt % NaCl equiv. Compositions (1) and (2) coexisted in the mineral-forming system at 250–350°C and 1.1–2.4 kbar as products of phase separation under conditions of decreasing P and T. The interaction of this fluid with host rocks resulted in the formation of extensive halos of beresitized rocks with sulfide disseminations. The precipitation of arsenopyrite and pyrite led to the substantial depletion of mineral-forming fluid in H₂S and destabilization of the Au(HS)²⁻ complex. The fluid with the third composition arose due to the boiling of the H₂O-CO₂-CH₄-NaCl-MgCl₂ liquid and was responsible for metasomatic alteration of host rocks. The late mineral assemblages were deposited from this fluid at the initial stage of ore formation. The high methane concentrations in the ore-forming fluid were likely caused by interaction of hydrothermal ore-bearing solutions with carbonaceous host rocks. The δ¹⁸O values of quartz from quartz-scheelite-pyrite-arsenopyrite and sulfide-sulfosalt mineral assemblages vary from +11.6 to +14.1‰ and +11.2 to +13.5‰, respectively. The parental fluids of the early and late mineral assemblages probably were derived from a magmatic source and were characterized by = +6.3 to +8.8‰ at 350°C and +3.6 to +5.9‰ at 280°C, respectively. The narrow interval of oxygen isotopic compositions shows that this source was homogeneous. The data obtained allow us to suggest that the deposit formation was related to magmatic activity, including the direct supply of ore components from a magma chamber and mobilization of these components in the processes of dehydration and decarbonation during contact and regional metamorphism. Original Russian Text ? N.A. Goryachev, O.V. Vikent’eva, N.S. Bortnikov, V.Yu. Prokof’ev, V.A. Alpatov, V.V. Golub, 2008, published in Geologiya Rudnykh Mestorozhdenii, 2008, Vol. 50, No. 5, pp. 414–444.