Fluid evolution of rare-element and muscovite granitic pegmatites from central Galicia, NW Spain

Fluid inclusions have been studied in three pegmatite fields in Galicia, NW Iberian Peninsula. Based on microthermometry and Raman spectroscopy, eight fluid systems have been recognized. The first fluid may be considered to be a pegmatitic fluid which is represented by daughter mineral (silicates)-rich aqueous inclusions. These inclusions are primary and formed above 500 °C (dissolution of daughter minerals). During pegmatite crystallization, this fluid evolved to a low-density, volatile-rich aqueous fluid with low salinity (93% H₂O; 5% CO₂; 0.5% CH₄; 0.2% N₂; 1.3% NaCl) at minimum P–T conditions around 3 ± 0.5 kbar and 420 °C. This fluid is related to rare-metal mineralization. The volatile enrichment may be due to mixing of magmatic fluids and fluids equilibrated with the host rock. A drop in pressure from 3 ± 0.5 to 1 kbar at a temperature above 420 °C, which may be due to the transition from predominantly lithostatic to hydrostatic pressure, is recorded by two-phase, water-rich inclusions with a low-density vapour phase (CO₂, CH₄ and N₂). Another inclusion type is represented by two-phase, vapour-rich inclusions with a low-density vapour phase (CO₂, CH₄ and N₂), indicating a last stage of decreasing temperature (360 °C) and pressure (around 0.5 kbar), probably due to progressive exhumation. Finally, volatile (CO₂)-rich aqueous inclusions, aqueous inclusions (H₂O-NaCl) and mixed-salt aqueous inclusions with low Th, are secondary in charac- ter and represent independent episodes of hydrothermal fluid circulation below 310 °C and 0.5 kbar. Received: 14 October 1999 / Accepted: 5 October 1999     

Phase equilibria in fluid inclusions from the Khtada Lake metamorphic complex

The Khtada Lake. British Columbia, metamorphic complex consists of high grade amphibolite and metasedimentary units with development of gneiss, migmatite and homogeneous autochthonous plutons. Maximum metamorphic conditions are estimated to have exceeded 5 kbar and 700°C.Fluid inclusions in matrix quartz are highly variable in density and composition, ranging from apparently pure CO₂ (gas or liquid or both at room temperature) through CO₂ + H₂O ± CH₄ mixtures to inclusions which are entirely aqueous. They occur along cracks, in groups without planar features and as isolated inclusions. The latter and some which occur in groups, are interpreted to most nearly approximate, in density and composition, the fluids present during the peak of metamorphism.The density and fluid composition data are derived from direct observations of phase changes between ? 180 and + 380°C and from the application of published experimental data in the system CH₄-CO₂-H₂O-NaCl. The most dense, pure CO₂ inclusions indicate a pressure of entrapment at 5 kbar, if a temperature of 700°C is assumed. This is in close agreement with the minimum P-T estimates from the mineral assemblages. Methane was positively identified in inclusions in graphite-bearing specimens. Salt content is concluded to be about 5–6 wt% NaCl equivalent in the aqueous phase in both aqueous and CO₂ + H₂O inclusions. There is evidence of immiscible separation of CO₂-rich and H₂O-rich fluids at temperatures at least as high as 375°C.     

Thermodynamic modeling of binary CH4-H2O fluid inclusions

This work reports the application of thermodynamic models, including equations of state, to binary (salt-free) CH₄-H₂O fluid inclusions. A general method is presented to calculate the compositions of CH₄-H₂O inclusions using the phase volume fractions and dissolution temperatures of CH₄ hydrate. To calculate the homogenization pressures and isolines of the CH₄-H₂O inclusions, an improved activity-fugacity model is developed to predict the vapor-liquid phase equilibrium. The phase equilibrium model can predict methane solubility in the liquid phase and water content in the vapor phase from 273 to 623 K and from 1 to 1000 bar (up to 2000 bar for the liquid phase), within or close to experimental uncertainties. Compared to reliable experimental phase equilibrium data, the average deviation of the water content in the vapor phase and methane solubility in the liquid phase is 4.29% and 3.63%, respectively. In the near-critical region, the predicted composition deviations increase to over 10%. The vapor-liquid phase equilibrium model together with the updated volumetric model of homogenous (single-phase) CH₄-H₂O fluid mixtures (Mao S., Duan Z., Hu J. and Zhang D. (2010) A model for single-phase PVTx properties of CO₂-CH₄-C₂H₆-N₂-H₂O-NaCl fluid mixtures from 273 to 1273 K and from 1 to 5000 bar. Chem. Geol.275, 148-160), is applied to calculate the isolines, homogenization pressures, homogenization volumes, and isochores at specified homogenization temperatures and compositions. Online calculation is on the website: http://www.geochem-model.org/.     

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

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

Synthetic fluid inclusions in natural quartz. III. Determination of phase equilibrium properties in the system H2O-NaCl to 1000°C and 1500 bars

Phase equilibria in the system H₂O-NaCl have been determined to 1000°C and 1500 bars using synthetic fluid inclusions formed by healing fractures in inclusion-free Brazilian quartz in the presence of the two coexisting, immiscible H₂O-NaCl fluids at various temperatures and pressures. Petrographic and microthermometric analyses indicate that the inclusions trapped one or the other of the two fluids present, or mixtures of the two. Salinities of the two coexisting phases were obtained from heating and freezing studies on those inclusions which trapped only a single, homogeneous fluid phase.Results of the present study are consistent with previously published data on the H₂O-NaCl system at lower temperatures and pressures, and indicate that the two-phase field extends well into the P-T range of most shallow magmatic-hydrothermal activity. As a consequence, chloride brines exsolved from many epizonal plutons during the process of “second-boiling” should immediately separate into a high-salinity liquid phase and a lower salinity vapor phase and produce coexisting halite-bearing and vapor-rich fluid inclusions. This observation is consistent with results of numerous fluid inclusion studies of ore deposits associated with shallow intrusions, particularly the porphyry copper deposits, in which halite-bearing and coexisting vapor-rich inclusions are commonly associated with the earliest stages of magmatic-hydrothermal activity.     

Role of fluids in migmatites: CO2-H2O fluid inclusions in leucosomes from the Deep Freeze Range migmatites (Terra Nova Bay, Antarctica)

ABSTRACT The metasedimentary sequence of the Deep Freeze Range (northern Victoria Land, Antarctica) experienced high-T/low-F metamorphism during the Cambro-Ordovician Ross orogeny. The reaction Bt + Sil + Qtz = Grt + Crd + Kfs + melt was responsible for the formation of migmatites. Peak conditions were c. 700–750° C, c. 3.5–5 kbar and x_H2Oc. 0.5). Distribution of fluid inclusions is controlled by host rock type: (1) CO₂-H₂O fluid inclusions occur only in graphite-free leucosomes; (2) CO₂–CH₄± H₂O fluid inclusions are the most common type in leucosomes, and in graphite-bearing mesosomes and gneiss; and (3) CO₂–N₂–CH₄ fluid inclusions are observed only in the gneiss, and subordinately in mesosomes. CO₂–H₂O mixtures (41% CO₂, 58% H₂O, 1% Nad mol.%) are interpreted as remnants of a synmig-matization fluid; their composition and density are compatible P–T–a_H2O conditions of migmatization (c. 750° C, c. 4 kbar, x_H2Oc. 0.5). CO₂-H₂O fluid in graphite-free leucosomes cannot originate via partial melting of graphite-bearing mesosomes in a closed system; this would have produced a mixed CO₂–CH₄ fluid in the leucosomes by a reaction such as Bt + Sil + Qtz + C ± H₂O = Grt + Crd + Kfs + L + CO₂+ CH₄. We conclude that an externally derived oxidizing CO₂-H₂O fluid was present in the middle crust and initiated anatexis. High-density CO₂-rich fluid with traces of CH₄ characterizes the retrograde evolution of these rocks at high temperatures and support isobaric cooling (P–T anticlockwise path). In unmigmatized gneiss, mixed CO₂–N₂–CH₄ fluid yields isochores compatible with peak metamorphic conditions (c. 700–750° C, c. 4–4.5 kbar); they may represent a peak metamorphic fluid that pre-dated the migmatization.     

A unified equation for calculating methane vapor pressures in the CH4-H2O system with measured Raman shifts

A unified equation has been derived by using all available data for calculating methane vapor pressures with measured Raman shifts of C-H symmetric stretching band (υ₁) in the vapor phase of sample fluids near room temperature. This equation eliminates discrepancies among the existing data sets and can be applied at any Raman laboratory. Raman shifts of C-H symmetric stretching band of methane in the vapor phase of CH₄-H₂O mixtures prepared in a high-pressure optical cell were also measured at temperatures between room temperature and 200 °C, and pressures up to 37 MPa. The results show that the CH₄υ₁ band position shifts to higher wavenumber as temperature increases. We also demonstrated that this Raman band shift is a simple function of methane vapor density, and, therefore, when combined with equation of state of methane, methane vapor pressures in the sample fluids at elevated temperatures can be calculated from measured Raman peak positions. This method can be applied to determine the pressure of CH₄-bearing systems, such as methane-rich fluid inclusions from sedimentary basins or experimental fluids in hydrothermal diamond-anvil cell or other types of optical cell.     

Methane-rich fluid inclusions in skarn near the giant REE–Nb–Fe deposit at Bayan Obo, Northern China

We report fluid inclusion data for skarn, formed at the contact between Hercynian granitoids and dolomite of the Proterozoic Bayan Obo Group, in the vicinity of Bayan Obo REE–Nb–Fe deposit, Inner Mongolia, China. Three types of fluid inclusions are identified: two-phase CH₄-rich, three-phase liquid–vapour–solid and two-phase aqueous inclusions. Using microthermometry and laser Raman microprobe analysis to calculate isochores for CH₄-bearing inclusions, we estimate fluid trapping conditions at T=280 to 344 °C and P<1 to 2.3 kbar. Such conditions are compatible with formation of CH₄ inclusions as a result of reaction between graphite in the country rocks (black slate sequence) and fluids derived from magma. The lack of carbonaceous material in the inclusions supports the hypothesis that CH₄ was generated during fluid migration rather than by in situ reaction. In contrast to the skarn, and despite the fact that similar graphite-bearing slates are found in the host rocks, no CH₄-bearing inclusions have been so far reported from Bayan Obo REE ores. We therefore conclude that the skarn-forming fluids in the contact aureole of the Hercynian granitoids were not involved at any stage in the formation of the Bayan Obo deposit.     

Experimental determination and analysis of the solubility of corundum in 0.1-molal CaCl2 solutions between 400 and 600°C at 0.6 to 2.0 kbar

Corundum (α-Al₂O₃) solubility was measured in 0.1-molal CaCl₂ solutions from 400 to 600°C between 0.6 and 2.0 kbar. The Al molality at 2 kbar increases from 3.1 × 10⁻⁴ at 400°C to 12.7 × 10⁻⁴ at 600°C. At 1 kbar, the solubility increases from 1.5 × 10⁻⁴m at 400°C to 3.4 × 10⁻⁴m at 600°C. These molalities are somewhat less than corundum solubility in pure H₂O (Walther, 1997) at 400°C but somewhat greater at 600°C. The distribution of species was computed considering the Al species Al(OH)₃⁰ and Al(OH)₄⁻, consistent with the solubility of corundum in pure H₂O of Walther (1997) and association constants reported in the literature. The calculated solubility was greater than that measured except at 600°C and 2.0 kbar, indicating that neutral-charged species interactions are probably important.A Setchénow model for neutral species resulted in poor fitting of the measured values at 1.0 kbar. This suggests that Al(OH)₃⁰ has a greater stability relative to Al(OH)₄⁻ than given by the models of Pokrovskii and Helgeson (1995) or Diakonov et al. (1996). The significantly lower Al molalities in CaCl₂ relative to those in NaCl solutions at the same concentration confirm the suggestions of Walther (2001) and others that NaAl(OH)₄⁰ rather than an Al-Cl complex must be significant in supercritical NaCl solutions to give the observed increase in corundum solubility with increasing NaCl concentrations.     

Characterization of fluid inclusions encaged in quartz veins of Parsoi Formation,central India

The study focuses on analysis of primary and secondary fluid inclusions present in quartz veins hosted in the phyllites to explore the stress and temperature conditions at the time of formation of metasediment sequences of the of Parsoi Formation, central India. The results reveal the two-phase liquid-rich fluid inclusions that indicate that the intrusions of quartz veins in phyllite may have taken place between the temperature from 168.8°C to 256.3°C with an average of 205.55°C from a magmatic moderately saline fluid (3.7 to 18.29 wt. % NaCl equiv.). The final ice-melting temperatures ranges from -14.6°C to -2.2°C which indicate that the aqueous fluids are mainly H₂O-NaCl. The density distribution of fluid inclusions rich in liquid H₂O only are unimodel and low in natures and appears to be entrapped between pressure 1.666 to 2.125 kbar at depth of 200m. The study supports epithermal nature of fluid inclusions. The characteristic of fluid inclusions along with lithological and structural peculiarities, nature of structural features may be helpful in exploring the future potential zone of gold mineralization in similar types of area.     

Fluid inclusion constraints on the uplift history of the metamorphosed massive sulphide deposits at Ducktown, Tennessee

Abstract Standard petrographic, microthermometric and Raman spectroscopic analyses of fluid inclusions from the metamorphosed massive sulphide deposits at Ducktown, Tennessee, indicate that fluids with a wide range of compositions in the C–O–H–N–S–salt system were involved in the syn- to post-metamorphic history of these deposits. Primary fluid inclusions from peak metamorphic clinopyroxene contain low-salinity, H₂O–CH₄ fluids and calcite, quartz and pyrrhotite daughter crystals. Many of these inclusions exhibit morphologies resembling those produced in laboratory experiments in which confining pressures significantly exceed the internal pressures of the inclusions. Secondary inclusions in metamorphic quartz from veins, pods, and host matrix record a complex uplift history involving a variety of fluids in the C–O–H–N–salt system. Early fluids were generated by local devolatilization reactions while later fluids were derived externally. Isochores calculated for secondary inclusions in addition to the chronology of trapping and morphological features of primary and secondary fluid inclusions suggest an uplift path which was concave toward the temperature axis over the P–T range 6–3 kbar and 550–225° C. Immiscible H₂O–CH₄–N₂–NaCl fluids were trapped under lithostatic to hydrostatic pressure conditions at 3–0.5 kbar and 215 ± 20° C. Entrapment occurred during Alleghanian thrusting, and the fluids may have been derived by tectonically driven expulsion of pore fluids and thermal maturation of organic material in lower-plate sedimentary rocks which are thought to underlie the deposits. Episodic fracturing and concomitant pressure decreases in upper-plate rocks, which host the ore bodies, would have allowed these fluids to move upward and become immiscible. Post-Alleghanian uplift appears to have been temperature-convex. Uplift rates of 0.10–0.05 mm year^?1 from middle Ordovician to middle Silurian – late Devonian, and 0.07–0.12 mm year^?1 from middle Silurian – late Devonian to late Permian are suggested by our uplift path and available geochronological data.     

Fluid inclusion and stable isotope (O, H, C, and S) constraints on the genesis of the Serrinha gold deposit, Gurupi Belt, northern Brazil

The Serrinha gold deposit of the Gurupi Belt, northern Brazil, belongs to the class of orogenic gold deposits. The deposit is hosted in highly strained graphitic schist belonging to a Paleoproterozoic (∼2,160 Ma) metavolcano-sedimentary sequence. The ore-zones are up to 11 m thick, parallel to the regional NW–SE schistosity, and characterized by quartz-carbonate-sulfide veinlets and minor disseminations. Textural and structural data indicate that mineralization was syn- to late-tectonic and postmetamorphic. Fluid inclusion studies identified early CO₂ (CH₄-N₂) and CO₂ (CH₄-N₂)-H₂O-NaCl inclusions that show highly variable phase ratios, CO₂ homogenization, and total homogenization temperatures both to liquid and vapor, interpreted as the product of fluid immiscibility under fluctuating pressure conditions, more or less associated with postentrapment modifications. The ore-bearing fluid typically has 18–33mol% of CO₂, up to 4mol% of N₂, and less than 2mol% of CH₄ and displays moderate to high densities with salinity around 4.5wt% NaCl equiv. Mineralization occurred around 310 to 335°C and 1.3 to 3.0 kbar, based on fluid inclusion homogenization temperatures and oxygen isotope thermometry with estimated oxygen fugacity indicating relatively reduced conditions. Stable isotope data on quartz, carbonate, and fluid inclusions suggest that veins formed from fluids with δ¹⁸O_H2O and δD_H2O (310–335°C) values of +6.2 to +8.4‰ and −19 to −80‰, respectively, which might be metamorphic and/or magmatic and/or mantle-derived. The carbon isotope composition (δ¹³C) varies from −14.2 to −15.7‰ in carbonates; it is −17.6‰ in fluid inclusion CO₂ and −23.6‰ in graphite from the host rock. The δ³⁴S values of pyrite are −2.6 to −7.9‰. The strongly to moderately negative carbon isotope composition of the carbonates and inclusion fluid CO₂ reflects variable contribution of organic carbon to an originally heavier fluid (magmatic, metamorphic, or mantle-derived) at the site of deposition and sulfur isotopes indicate some oxidation of the originally reduced fluid. The deposition of gold is interpreted to have occurred mainly in response to phase separation and fluid-rock interactions such as CO₂ removal and desulfidation reactions that provoked variations in the fluid pH and redox conditions.     

Production of carbonic fluids during metamorphism of graphitic pelites in a collisional orogen—An assessment from fluid inclusions

Fluid inclusions in quartz veins within Proterozoic metamorphic rocks in the Black Hills, South Dakota, were examined by microthermometry and Raman spectroscopy to assess the evolution of fluid compositions during regional metamorphism of organic-rich shales and late-orogenic magmatism, both of which were related to the collision of the Wyoming and Superior crustal blocks. Fluid inclusions occur in veins that began to be generated before or during regional compression and metamorphism that reached at least garnet-grade conditions, and in veins within the aureole of the Harney Peak Granite (HPG), where temperatures reached second-sillimanite grade conditions. Early veins in the schists have undergone recrystallization during heating and deformation that modified the composition of early CH₄ or CO₂ and N₂-dominated inclusions. These fluids were apparently trapped under conditions of immiscibility with a saline aqueous fluid phase. They are interpreted to represent components generated during maturation of organic matter and dehydration of phyllosilicates during incipient metamorphism at reducing fO₂ conditions. Most inclusions in the quartz veins are, however, secondary CO₂-bearing. They imply a transition to higher fO₂ conditions with increasing temperature of regional metamorphism. The fO₂ conditions may have been controlled by the mineral assemblage in the host metapelites. The prevalence of bimodal distributions of trapped CO₂-N₂ and aqueous endmembers in the biotite and garnet zones also suggests that two immiscible fluid phases existed during the regional metamorphism.In the aureole of the HPG, graphite was evidently consumed by influx of magmatic fluids. CO₂-H₂O fluid inclusions dominate, but they have significantly less N₂ than inclusions at lower metamorphic grades. All inclusions define secondary trails in mostly unstrained quartz. The bimodality of inclusion compositions is not as well defined as at lower grades, with many inclusions containing intermediate CO₂-H₂O compositions. This suggests that a single fluid phase existed at the high temperatures in the granite aureole, but then unmixed during cooling. A set of late quartz veins with graphitized and tourmalinized selvages in the granite aureole contains CH₄-bearing inclusions with little N₂. The existence of CH₄ in these inclusions is attributed to complexing of magmatic B with hydroxyl anions taken from the CO₂-H₂O fluid phase, effectively causing reduction in fO₂ and promoting precipitation of graphite.     

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.     

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

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

Crystallization conditions and evolution of magmatic fluids in the Harney Peak Granite and associated pegmatites, Black Hills, South Dakota—Evidence from fluid inclusions

A microthermometric study of inclusions in granites and pegmatites in the Proterozoic Harney Peak Granite system identified four types of inclusions. Type 1 inclusions are mixtures of CO₂ and H₂O and have low salinities, on average 3.5 wt.% NaCl_eq; type 2 inclusions are aqueous solutions of variable salinities, from 0 to 40% wt.% NaCl_eq; type 3 inclusions are carbonic, dominated by CO₂, with no detectable water; and type 4 inclusions consist of 20 to 100% solids, with the remaining volume occupied by a CO₂-H₂O fluid. Many inclusions have a secondary character; however, a primary character can be unambiguously established in several occurrences of the type 1 inclusions. These inclusions were trapped above the solidus and represent the exsolved magmatic fluid. The secondary populations of types 1, 2, and 3 probably formed as a result of reequilibration and unmixing of the type 1 fluid that progressively changed composition and density with decreasing temperature and pressure and was finally trapped along healed microfractures under subsolidus conditions. Type 4 inclusions are primary and are interpreted to be trapped, fluid-bearing, complex silicate melts that subsequently solidified or underwent other posttrapping changes.It is demonstrated that primary type 1 fluid inclusions that coexist with crystallized melt inclusions in the complex, Li-bearing Tin Mountain pegmatite were trapped along the two-fluid phase boundary in the system CO₂-H₂O-NaCl_eq. Consequently, the temperature and pressure conditions of trapping are identical to the bulk homogenization conditions—on average 340°C and 2.7 kbar. These conditions indicate that this Li-, Cs-, Rb-, P-, and B-rich pegmatite crystallized at some of the lowest known temperatures for a silicate melt in the crust. An internally consistent, empirical solvus surface in P-T-X_CO2 coordinates was generated for the pseudobinary CO₂-(H₂O-4.3 wt.% NaCl_eq) pegmatite fluid system. Distribution coefficients for the major species CO₂, H₂O, NaCl, and CH₄ between the immiscible CO₂-rich and H₂O-rich fluid phases as a function of pressure and temperature were extracted from data for the two cogenetic fluid inclusions types.     

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.     

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

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

Fluid 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     

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.