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/.     

Applications of the SW96 formulation in the thermodynamic calculation of fluid inclusions and mineral-fluid equilibria

The SW96 formulation explicit in Helmholtz free energy proposed by Span and Wagner (1996) is the most accurate multifunction equation of state of CO₂ fluid, from which all thermodynamic properties can be obtained over a wide temperature-pressure range from 216.592 to 1100 K and from 0 to 8000 bar with or close to experimental accuracy. This paper reports the applications of the SW96 formulation in fluid inclusions and mineral-fluid equilibria. A reliable and highly efficient algorithm is presented for the saturated properties of CO₂ so that the formulation can be conveniently applied in the study of fluid inclusions, such as calculation of homogenization pressures, homogenization densities (or molar volumes), volume fractions of vapor phase and isochores. Meanwhile, the univariant curves of some typical decarbonation reactions of minerals are calculated with the SW96 formulation and relevant thermodynamic models of minerals. The computer code of the SW96 formulation can be obtained from the corresponding author.     

Fluid Characteristics and Evolution of the Zhawulong Granitic Pegmatite Lithium Deposit in the Ganzi‐Songpan Region,Southwestern China

The Zhawulong granitic pegmatite lithium deposit is located in the Ganzi-Songpan orogenic belt. Fluid inclusions in spodumene and coexisting quartz were studied to understand the cooling path and evolution of fluid within albite–spodumene pegmatite. There are three distinguishable types of fluid inclusions: crystal-rich, CO2–NaCl–H2O, and NaCl–H2O. At more than 500°C and 350~480 MPa, crystal-rich fluid inclusions were captured during the pegmatitic magma-hydrothermal transition stage, characterized by a dense hydrous alkali borosilicate fluid with a carbonate component. Between 412°C and 278°C, CO2–NaCl–H2Ofluid inclusions developed in spodumene (I) and quartz (II) with a low salinity (3.3–11.9 wt%NaCl equivalent) and a high volatile content, which represent the boundary between the transition stage and the hydrothermal stage. The subsequentNaCl–H2Ofluid inclusions from the hydrothermal stage, between 189°C and 302°C, have a low salinity (1.1–13.9 wt%NaCl equivalent). The various types of fluid inclusions reveal the P–T conditions of pegmatite formation, which marks the transition process from magmatic to hydrothermal. The ore-forming fluids from the Zhawulong deposit have many of the same characteristics as those from the Jiajika lithium deposit. The ore-forming fluid provided not only materials for crystallization of rare metal minerals, such as spodumene and beryl, but also the ideal conditions forthe growth of ore minerals. Therefore, this area has favorable conditions for lithium enrichment and excellent prospecting potential.     

Compositional zoning of fluid inclusions in the Archaean Junction gold deposit,Western Australia: A process of fluid ‐ wall‐rock interaction?

The Junction gold deposit, in Western Australia, is an orogenic gold deposit hosted by a differentiated, iron‐rich, tholeiitic dolerite sill. Petrographic, microthermometric and laser Raman microprobe analyses of fluid inclusions from the Junction deposit indicate that three different vein systems formed at three distinct periods of geological time, and host four fluid‐inclusion populations with a wide range of compositions in the H₂O–CO₂–CH₄–NaCl ± CaCl₂ system. Pre‐shearing, pre‐gold, molybdenite‐bearing quartz veins host fluid inclusions that are characterised by relatively consistent phase ratios comprising H₂O–CO₂–CH₄ ± halite. Microthermometry suggests that these veins precipitated when a highly saline, >340°C fluid mixed with a less saline ≥150°C fluid. The syn‐gold mineralisation event is hosted within the Junction shear zone and is associated with extensive quartz‐calcite ± albite ± chlorite ± pyrrhotite veining. Fluid‐inclusion analyses indicate that gold deposition occurred during the unmixing of a 400°C, moderately saline, H₂O–CO₂ ± CH₄ fluid at pressures between 70 MPa and 440 MPa. Post‐gold quartz‐calcite‐biotite‐pyrrhotite veins occupy normal fault sets that slightly offset the Junction shear zone. Fluid inclusions in these veins are predominantly vapour rich, with CO₂?CH₄. Homogenisation temperatures indicate that the post‐gold quartz veins precipitated from a 310 ± 30°C fluid. Finally, late secondary fluid inclusions show that a <200°C, highly saline, H₂O–CaCl₂–NaCl–bearing fluid percolated along microfractures late in the deposit's history, but did not form any notable vein type. Raman spectroscopy supports the microthermometric data and reveals that CH₄–bearing fluid inclusions occur in syn‐gold quartz grains found almost exclusively at the vein margin, whereas CO₂–bearing fluid inclusions occur in quartz grains that are found toward the centre of the veins. The zonation of CO₂:CH₄ ratios, with respect to the location of fluid inclusions within the syn‐gold quartz veins, suggest that the CH₄ did not travel as part of the auriferous fluid. Fluid unmixing and post‐entrapment alteration of the syn‐gold fluid inclusions are known to have occurred, but cannot adequately account for the relatively ordered zonation of CO₂:CH₄ ratios. Instead, the late introduction of a CH₄–rich fluid into the Junction shear zone appears more likely. Alternatively, the process of CO₂ reduction to CH₄ is a viable and plausible explanation that fits the available data. The CH₄–bearing fluid inclusions occur almost exclusively at the margin of the syn‐gold quartz veins within the zone of high‐grade gold mineralisation because this is where all the criteria needed to reduce CO₂ to CH₄ were satisfied in the Junction deposit.     

Size effect in metastable water

We experimentally determined the maximum tension in synthetic fluid inclusions from the difference between the temperatures of homogenization (T _h) and spontaneous vapor nucleation (T _n). At temperatures of 100–200°C, liquid water may exist at negative pressures of up to 100–150 MPa. Owing to an increase in surface tension, the effect is even more significant in salt solutions and occurs at higher temperatures. A decrease in the linear dimension of fluid phase by an order of magnitude and, correspondingly, a three orders of magnitude decrease in volume (which is proportional to R ₃) increase the maximum tension by ～25MPa. Tension in the liquid phase of water-salt systems may be higher than ~200 MPa without cavitation. Metastability of water and salt solutions in small-sized vacuoles generates stresses in the fluid-mineral system resulting in high solubilities of solid phases. An increase in volume due to coalescence of small inclusions or vanishing of metastability results in an abrupt decrease in supersaturation.     

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

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

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.     

Crystallization conditions of peraluminous charnockites: constraints from mineral thermometry and thermodynamic modelling

Most igneous charnockites are interpreted to have crystallized at hot and dry conditions, i.e. at >800?°C and <3 wt.% H₂O and with an important CO₂ component in the system. These charnockites are metaluminous to weakly peraluminous and their formation involves a significant mantle-derived component. This study, in contrast, investigates the crystallization conditions of strongly peraluminous, metasediment-sourced charnockites from the Qinzhou Bay Granitic Complex, South China. To constrain the temperature-melt H₂O crystallization paths for the studied peraluminous charnockites, petrographic characterization was combined with fluid inclusion compositional data, mineral thermometry, and thermodynamic modelling. The uncertainties of the thermodynamic modelling in reconstructing the crystallization conditions of the granitic magmas have been evaluated by comparison between modelled and experimental phase relations for a moderately evolved, peraluminous granite (~70 wt.% SiO₂). The comparison suggests that the modelling reproduces the experimentally derived phase saturation boundaries with uncertainties of 20–60?°C and 0.5–1 wt.% H₂O for systems with ≤1–2 wt.% initial melt H₂O at ~0.2 GPa. For the investigated natural systems, the thermometric estimates and modelling indicate that orthopyroxene crystallized at relatively low temperature (750–790?±?30?°C) and moderately high to high melt H₂O content (3.5–5.6?±?0.5 wt.%). The charnockites finally solidified at relatively “cold” and “wet” conditions. This suggests that thermodynamic modelling affords a possible approach to constrain charnockite crystallization as tested here for peraluminous, moderately low pressure (≤0.3 GPa), and overall H₂O-poor systems (≤1–2 wt.% H₂O total), but yields results with increasing uncertainty for high-pressure or H₂O-rich granitic systems.     

Mineral compositions and fluid evolution of the Tonglushan skarn Cu–Fe deposit,SE Hubei,east-central China

The Tonglushan Cu–Fe deposit (1.12 Mt at 1.61% Cu, 5.68 Mt at 41% Fe) is located in the westernmost district of the Middle–Lower Yangtze River metallogenic belt. As a typical polymetal skarn metallogenic region, it consists of 13 skarn orebodies, mainly hosted in the contact zone between the Tonglushan quartz-diorite pluton (140 Ma) and Lower Triassic marine carbonate rocks of the Daye Formation. Four stages of mineralization and alterations can be identified: i.e. prograde skarn formation, retrograde hydrothermal alteration, quartz-sulphide followed by carbonate vein formation. Electron microprobe analysis (EMPA) indicates garnets vary from grossular (Ad_20.2–41.6Gr_49.7–74.1) to pure andradite (Ad_47.4–70.7Gr_23.9–45.9) in composition, and pyroxenes are represented by diopsides. Fluid inclusions identify three major types of fluids involved during formation of the deposit within the H₂O–NaCl system, i.e. liquid-rich inclusions (Type I), halite-bearing inclusions (Type II), and vapour-rich inclusions (Type III). Measurements of fluid inclusions reveal that the prograde skarn minerals formed at high temperatures (>550°C) in equilibrium with high-saline fluids (>66.57 wt.% NaCl equivalent). Oxygen and hydrogen stable isotopes of fluid inclusions from garnets and pyroxenes indicate that ore-formation fluids are mainly of magmatic-hydrothermal origin (δ¹⁸O = 6.68‰ to 9.67‰, δD = –67‰ to –92‰), whereas some meteoric water was incorporated into fluids of the retrograde alteration stage judging from compositions of epidote (δ¹⁸O = 2.26‰ to 3.74‰, δD= –31‰ to –73‰). Continuing depressurization and cooling to 405–567°C may have resulted in both a decrease in salinity (to 48.43–55.36 wt.% NaCl equivalent) and the deposition of abundant magnetite. During the quartz-sulphide stage, boiling produced sulphide assemblage precipitated from primary magmatic-hydrothermal fluids (δ¹⁸O = 4.98‰, δD = –66‰, δ³⁴S values of sulphides: 0.71–3.8‰) with an extensive range of salinities (4.96–50.75 wt.% NaCl equivalent), temperatures (240–350°C), and pressures (11.6–22.2 MPa). Carbonate veins formed at relatively low temperatures (174–284°C) from fluids of low salinity (1.57–4.03 wt.% NaCl equivalent), possibly reflecting the mixing of early magmatic fluids with abundant meteoric water. Boiling and fluid mixing played important roles for Cu precipitation in the Tonglushan deposit.     

The role of chloride-carbonate melts in the formation of sideritic carbonatites of the KARASUg FE-F-REE deposit (Tyva Republic,Russia)

The authors have studied melt-fluid and fluid inclusions in quartz and fluorite of sideritic and ankerite-calcitic carbonatites of the Karasug ore field, as well as melt inclusions in apatite from granosyenites. The content of salt and fluid components in brine-melt inclusions was evaluated on the basis of the thermodynamic data, the calculations of volumes and densities of the solid phases, a solution of about 50% concentration, and the gas phase of the inclusions, as well as the results of the LA-ICP-MS analysis. The content of salt phases, the solution, and the gas phase amounted to 85–70, 10–25, and about 5% of the inclusion substance, respectively. The total percentage of salt and fluid components (H₂O and CO₂) amounted to 90–80 and 10–20 wt %, respectively. The fraction of a carbonate constituent in the inclusions was as high as 45–50% and over in ankerite-calcite carbonatites and about 15 wt % in sideritic carbonatites. The 117.2 ± 1.3 Ma age of these carbonatites by ⁴⁰Ar/³⁹Ar, along with other datings for this area, shows that their formation was associated with a manifestation of the Cretaceous alkaline-mafic magmatism (117–120 Ma). The presented model of the formation of carbonatites is in agreement with the sequence of the development of magmatic processes and mineralization in this area. The model is also confirmed by the results of the studies of melt and fluid inclusions in minerals.     

Hydrothermal Fluid Evolution Associated with Gold Mineralization at the Wenyu Mine, Xiaoqinling District, China

Abstract: The Wenyu mesothermal gold deposit is located in the Xiaoqinling district about 1000 km southwest of Beijing in central China. It occurs in the Late Archean to Early Proterozoic metamorphosed volcanic and sedimentary rocks. Three distinct stages of veins have been identified: (I) gold‐poor quartz–pyrite veins, (II) gold‐rich sulfide–quartz veins, and (III) gold‐poor carbonate–quartz veins. Stage II can be subdivided into IIa and IIb. Gold typically occurs as fracture‐fillings associated with chalcopyrite and galena. Fluid inclusions were examined in quartz samples from veins of both stage I and II. Three types of fluid inclusions are identified: CO₂–H₂O, CO₂–rich, and aqueous inclusions. The first two types are of primary in origin. The last type occurs in two ways: coexisting with CO₂–H₂O and CO₂–rich inclusions and thus primary in origin; and occurring along late healed fractures and hence secondary in origin. CO₂–H₂O inclusions display progressively decreasing Th and increasing Thco₂, from the highest Th (311–408C) and lowest Thco₂ (average 18C) in stage I quartz through middle Th (284–358C) and ThCO₂(average 25C) in stage IIa quartz to the lowest Th (275–314C) and highest ThCO₂ (average 28C) in stage IIb quartz, indicating an evolving H₂O–CO₂–NaCl fluid system. CO₂–rich and primary aqueous inclusions show consistent ThCO₂ or Th with their coexistent CO₂–H₂O inclusions. Whereas the secondary aqueous inclusions in stage I and IIa quartz have almost the same Th and salinity as the primary aqueous inclusions in stage IIb quartz. Comparing with CO₂–H₂O inclusions, these non–CO₂, low salinity aqueous inclusions may come from different origin, most probably meteoric water. Unlike in both stage I and IIa quartz, fluid inclusions in stage IIb do not show evidence of fluid immiscibility. The fact that most of gold is associated with stage IIa and IIb veins and not with veins of stage I which is the main stage of vein formation suggests that gold deposition occurs at the later stage of fluid immiscibility. The continuing phase separation led to the deposition of large amounts of gold at the Wenyu mine.     

High-density nitrogen inclusions in barite from a giant siderite vein: implications for Alpine evolution of the Variscan basement of Western Carpathians, Slovakia

Contrasting compositions and densities of fluid inclusions were revealed in siderite–barite intergrowths of the Dro?diak polymetallic vein hosted in Variscan basement of the Gemeric unit (Central European Carpathians). Primary two‐phase aqueous inclusions in siderite homogenized between 101 and 165 °C, total salinity ranged between 18 and 27 wt%, and CaCl₂/(NaCl + CaCl₂) weight ratios were fixed at 0.1–0.3. By contrast, mono‐ and two‐phase aqueous inclusions in barite exhibited total salinities between 2 and 22 wt%, and the CaCl₂/NaCl ratios ranged from NaCl‐ to CaCl₂‐dominated compositions. The aqueous inclusions in barite were closely associated with very high‐density (0.55–0.745 g cm^?3) nitrogen inclusions, in some cases containing up to 16 mol.% CO₂. Crystallization P–T conditions of siderite (175–210 °C, 1.2–1.7 kbar) constrained by the vertical oxygen isotope gradient along the studied vein, isochores of fluid inclusions and the K/Na exchange thermometer corresponded to minimal palaeodepths between 4.3 and 6.3 km, assuming lithostatic load and average crust density of 2.75 g cm^?3. Maximum fluid pressure during barite crystallization attained 3.6–4.4 kbar at 200–300 °C, and the most dense nitrogen inclusions maintained without decrepitation the residual internal pressure of 2.2 kbar at 25 °C. Contrasting fluid compositions, increasing depths of burial (～4–14 km) and decreasing thermal gradients (～40–15 °C km^?1) during initial mineralization stages of the Dro?diak vein reflect Alpine orogenic processes, rather than an incipient Permian rifting suggested in previous metallogenetic models. Siderite crystallized at rising P–T in a closed, rock‐buffered hydrothermal system developed in the Variscan basement during the north‐vergent Cretaceous thrusting and thickening of the Gemeric crustal wedge. Variable salinities of the barite‐hosted inclusions reflect a fluid mixing in open hydrothermal system, and re‐equilibration textures (lengths of decrepitation cracks proportional to fluid inclusion sizes) correspond to retrograde crystallization trajectory coincidental with transpression or unroofing. Maximum recorded fluid pressures indicate ～12‐km‐thick pile of imbricated nappe units accumulated over the Gemeric basement during the Cretaceous collision.     

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

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

Unexpected phase assemblages in inclusions with ternary H2O-salt fluids at low temperatures

Phase assemblages and temperatures of phase changes provide important information about the bulk properties of fluid inclusions, and are typically obtained by microthermometry. Inclusions are synthesized in natural quartz containing an aqueous fluid with a composition in the ternary systems of H₂O-NaCl₂-CaCl₂, H₂O-NaCl-MgCl₂, and H₂O-CaCl₂-MgCl₂. This study reveals that these fluid inclusions may behave highly unpredictably at low temperatures due to the formation of metastable phase assemblages. Eutectic temperatures cannot be detected in most of the fluid inclusions containing these ternary systems. Nucleation of a variety of solid ice and salt-hydrate phases in single fluid inclusions is often partly inhibited. Raman spectroscopy at low temperatures provides an important tool for interpreting and understanding microthermometric experiments, and visualizing stable and metastable phase assemblages. Final dissolution temperatures of ice, salt-hydrates, and salt must be treated with care, as they can only be interpreted by purely empirical or thermodynamic models at stable conditions.     

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.     

Geological and Fluid Inclusion Constraints on Gold Deposition Processes of the Dayingezhuang Gold Deposit,Jiaodong Peninsula,China

The Dayingezhuang gold deposit, hosted mainly by Late Jurassic granitoids on Jiaodong Peninsula in eastern China, contains an estimated 170 t of gold and is one of the largest deposits within the Zhaoping fracture zone. The orebodies consist of auriferous altered pyrite–sericite–quartz granites that show Jiaojia-type (i.e., disseminated and veinlet) mineralization. Mineralization and alteration are structurally controlled by the NE- to NNE-striking Linglong detachment fault. The mineralization can be divided into four stages: (K-feldspar)–pyrite–sericite–quartz, quartz–gold–pyrite, quartz–gold–polymetallic sulfide, and quartz–carbonate, with the majority of the gold being produced in the second and third stages. Based on a combination of petrography, microthermometry, and laser Raman spectroscopy, three types of fluid inclusion were identified in the vein minerals: NaCl–H2O (A-type), CO2–H2O–NaCl (AC-type), and pure CO2 (PC-type). Quartz crystals in veinlets that formed during the first stage contain mainly AC-type fluid inclusions, with rare PC-type inclusions. These fluid inclusions homogenize at temperatures of 251°C–403°C and have low salinities of 2.2–9.4 wt% NaCl equivalent. Quartz crystals that formed in the second and third stages contain all three types of fluid inclusions, with total homogenization temperatures of 216°C–339°C and salinities of 1.8–13.8 wt% NaCl equivalent for the second stage and homogenization temperatures of 195°C–321°C and salinities of 1.4–13.3 wt% NaCl equivalent for the third stage. In contrast, quartz crystals that formed in the fourth stage contains mainly A-type fluid inclusions, with minor occurrences of AC-type inclusions; these inclusions have homogenization temperatures of 106°C–287°C and salinities of 0.5–7.7 wt% NaCl equivalent. Gold in the ore-forming fluids may have changed from Au(HS)0 as the dominant species under acidic conditions and at relatively high temperatures and fO2 in the early stages, to Au(HS)2– under neutral-pH conditions at lower temperatures and fO2 in the later stages. The precipitation of gold and other metals is inferred to be caused by a combination of fluid immiscibility and water–rock interaction.     

Inclusions of magmatic fluids: P-V-T-X properties of aqueous salt solutions of various types and petrological implications

The P-V-T-X properties of H₂O-salt systems are compared depending on the solubility coefficient of compounds contained in these systems and the presence or absence of critical phenomena in the saturated solutions. Data on synthetic and natural inclusions captured in minerals at elevated temperatures and pressures and employed to discuss the principal features of phase diagrams of the H₂O-NaCl system (type I) and H₂O-NaF system (type II or P-Q type). It is demonstrated how characteristics of magmatic fluids of various types are manifested during the development of miarolitic pegmatites (Malkhan field in Transbaikalia) and during the crystallization of F-rich ongonitic melts (Ary-Bulak Massif in eastern Transbaikalia). Characteristics of solutions and gas-rich (gaseous) fluid inclusions in quartz phenocrysts from porphyritic ongonites (disappearance of the liquid regardless of its density and the overall salinity near the critical point of water, distinctive features of the dissolution of the crystalline phase, and the ability of the inclusions to withstand heating to 1400°C without decrepitation), and the richness of the fluid-magmatic system as a whole in F suggest that the ongonite melt crystallized in the presence of low-density NaF-bearing fluids of the P-Q type with a minor admixture of chlorides. It is important to identify the type of solutions in the fluid inclusions, because without knowing this type, it is impossible to accurately enough calculate the pressure at the temperatures of inclusion capture. For example, the unwarranted classification of solutions of type II (P-Q) in inclusions with the chloride system results in a significant overestimation of the calculated fluid pressures. A technique is proposed for studying the high-temperature immiscibility region in P-Q systems based on data obtained on gaseous fluid inclusions.     

Evolution of carbon dioxide-bearing saline fluids in the mantle wedge beneath the Northeast Japan arc

Lherzolite xenoliths containing fluid inclusions from the Ichinomegata volcano, located on the rear-arc side of the Northeast Japan arc, may be considered as samples of the uppermost mantle above the melting region in the mantle wedge. Thus, these fluid inclusions provide valuable information on the nature of fluids present in the sub-arc mantle. The inclusions in the Ichinomegata amphibole-bearing spinel–plagioclase lherzolite xenoliths were found to be composed mainly of CO₂–H₂O–Cl–S fluids. At equilibrium temperature of 920 °C, the fluid inclusions preserve pressures of 0.66–0.78 GPa, which correspond to depths of 23–28 km. The molar fraction of H₂O and the salinity of fluid inclusions are 0.18–0.35 and 3.71 ± 0.78 wt% NaCl equivalent, respectively. These fluid inclusions are not believed to be fluids derived directly from the subducting slab, but rather fluids exsolved from sub-arc basaltic magmas that are formed through partial melting of mantle wedge triggered by slab-derived fluids.     

Evolution of gas and aqueous fluid in low-permeability argillaceous rocks during uplift and exhumation of the central Swiss Alps

Fluid chemistry and the hydraulic regime in a marl formation of the Swiss Alps were studied by a number of techniques. Fluid inclusions record the conditions of maximum burial and regional low-temperature metamorphism, whereas fluid samples and hydraulic tests derived from deep boreholes reflect present-day, near-surface conditions. The characterization of the different types of fluids places constraints on the geochemical and hydraulic evolution of low-permeability argillaceous rocks during uplift and exhumation.Fluid inclusions were studied by microthermometry and sampled directly by decrepitation techniques. They contain a two-phase system consisting of an aqueous fluid and a coexisting CH₄-rich gas (T=190–250°C, P_lith≈2500 bar). Bulk and isotopic compositions of aqueous fluid inclusions are consistent with a mixture of connate seawater and water derived from the dehydration of clay minerals. Methane was generated in situ by thermal cracking of kerogen. Textural evidence and stable isotopic signatures of carbonates in veins and in the rock matrix indicate local buffering of fluid compositions and very low water/rock ratios. Free fluids residing in the present-day fracture and matrix porosity consist of CH₄-saturated Na–Cl groundwater with minute amounts of free CH₄ gas which occurs in druses. Their chemical and isotopic compositions are very similar to those of the fluid inclusions, suggesting a common origin. Post-metamorphic admixtures of externally derived waters cannot be identified, and it is suggested that present-day Na–Cl groundwaters that occur in the central parts of the marl have resided in the formation since the time of metamorphism some 20 Ma b.p. The only major change in the fluid composition has been the outgassing of CH₄ from the formation, most probably by diffusion.The hydraulic regime during metamorphism was characterized by localized fluid underpressures in open veins because widely scattered, sub-hydrostatic pressures were often identified in fluid inclusions. The central part of the argillaceous rock body, approximately coinciding with the region where Na–Cl groundwaters occur, has sub-hydrostatic pressures today, as indicated by hydraulic tests in deep boreholes.Both the closed-system behavior derived from the chemical and isotopic characteristics of the fluids and the (recurrent or continuous) existence of hydraulic underpressures suggest very low permeabilities of argillaceous rocks during metamorphism and throughout subsequent uplift and exhumation. All fluids present in the central parts of the formation are either connate or produced in situ. Even though major events of brittle faulting and unloading due to uplift occurred since the peak of metamorphism, fluid flow through the formation has been negligible.