CO2 Fluid Inclusions Research Articles

Deep syntectonic burial of the Anthracite belt, Eastern Pennsylvania

Fluid inclusion microthermometry and Raman spectroscopy of fluid inclusions in quartz veins from the Pennsylvanian rocks of the Anthracite belt, eastern Pennsylvania support a deep burial model of coalification in favor of focused orogenic hot fluid flow. High-temperature (250 to 255 °C) trapping of CH4 ± CO2 saturated aqueous fluids and CH4 ± CO2 inclusions indicate fluid trapping at depths of 11.5 to 13.4 km under a cover of Pennsylvanian to Permian(?) syntectonic load. In the folded rocks to the south of the Anthracite belt, CH4 ± CO2 fluid inclusions indicate a sediment load that was up to 16.3 km thick. Re-equilibrated aqueous fluid inclusions from veins in Silurian through Devonian rocks give the same range of trapping conditions but a wide range of fluid salinities suggesting that folding, fracturing, and meteoric recharge resulted in the intermixing of fluids from throughout the stratigraphic succession.

Source of Ore-Forming Fluids and Ore Genesis of the Batailing Au Deposit, Central Jilin Province, Northeast China: Constraints from Fluid Inclusions and H-O-C-S-Pb Isotopes

The Batailing Au deposit is a vein-type deposit in central Jilin Province, situated in the southern sector of the Lesser Xing’an–Zhangguangcai Range within the eastern Central Asian Orogenic Belt. NE-trending fault-controlled orebodies occur in the Upper Permian Yangjiagou Formation and quartz diorite–porphyrite. The mineralisation process was delineated into three stages: (I) quartz–arsenopyrite–pyrite, (II) quartz–polymetallic sulphides (main Au mineralisation stage), and (III) quartz–pyrite–carbonate. Fluid inclusions (FIs) in quartz were identified as four types: PC-type (pure CO2), C1-type (CO2-bearing), C2-type (CO2-rich), and W-type (aqueous two-phase). Raman spectroscopy analysis revealed that the vapor components of the FIs predominantly comprised CO2 with minor quantities of CH4 in stages I–II. Stages I and II encompassed four types of FIs with homogenisation temperature ranging from 264 to 332 °C and 213 to 292 °C and salinity spanning from 4.7 to 11.2 wt% and 1.8 to 11.6 wt%, respectively. Stage III exclusively contained W-type FIs with homogenisation temperature ranging from 152 to 215 °C and salinity spanning from 1.4 to 6.4 wt%. H-O isotopic values (δD = −84 to −79.6‰, δ18OH2O = 6.2 to 6.4‰ in stage I and δD = −96.4 to −90.4‰, δ18OH2O = 2.8 to 4.4‰ in stage II) and microthermometric data indicated that the ore-forming fluids are initially from a magmatic source, with later meteoric water input. Low C isotopic data from CO2 in FIs in quartz (−24.4 to −24.3‰ in stage I and −23.7 to −22.6‰ in stage II) indicated an organic carbon source. Ore precipitation is mainly attributable to fluid immiscibility. S-Pb isotopic data (δ34S = −3.5 to −1.6‰; 206Pb/204Pb = 18.325–18.362, 207Pb/204Pb = 15.523–5.562, 208Pb/204Pb = 38.064–38.221) revealed that ore metals primarily originated from magma. Based on this research, the origin of the Batailing Au deposit is of the mesothermal magmatic–hydrothermal lode type.

The helium and carbon isotopic signature of Ocean island basalts: Insights from Fogo volcano (Cape Verde archipelago)

Fluid inclusions (FI) entrapped in phenocrysts carried by Ocean Island Basalts (OIB) contain key information on volatiles’ abundance and origin in their mantle sources. Here, we add new piece of knowledge to our understanding of volatile geochemistry in global OIB magmas, by presenting new noble gas (He-Ne-Ar) and carbon (C) isotope results for olivine- and clinopyroxene-hosted FI from enclaves, lavas, tephra and volcanic gas samples from Fogo, the only frequently active volcano at the Cape Verde archipelago (eastern Atlantic Ocean). FI, together with crater fumaroles, constrain the Fogo 3He/4He signature at 7.14–8.44 Rc/Ra (where RC is the air-corrected 3He/4He isotope ratio, and Ra is the same ratio in air), which is within the typical MORB (Mid-Ocean Ridge Basalt) mantle. The carbon isotopic ratio (δ13C vs. Pee Dee Belemnite) of CO2 in FI and fumaroles range from -6.04 to -4.41 ‰. We identify systematic variations of δ13C and He/Ar* with FI entrapment pressure (estimated from a combination of host mineral barometry and FI microthermometry), from which we develop a model for volatile degassing in the mantle-to-crustal magma storage system. The model predicts a crustal-like signature for carbon (δ13C of -0.4 ± 1.0 ‰) in primary melts formed by mantle melting at ∼2200 MPa (∼77 km) and a source He/Ar* ratio of 0.90–0.24, which are indicative of variably depleted mantle metasomatized by carbon enriched melts/fluids from a crustal component. We also use our results to characterise regional (in the Cape Verde and Canary archipelagos) and global trends in C and He isotope composition from OIB. From a comparison with the few other OIB localities for which δ13C are available, we propose that a carbon enriched crustal component could be recurrent at a global scale in OIB magmatism, although often masked by isotope fractionation during magmatic degassing. We additionally find that, at regional scale, He isotopes in OIB scale inversely correlate with the degree of partial melting of the mantle beneath individual islands’ (inferred from the La/Yb ratio of erupted basalts). More widely, our results corroborate previously established global relationships between OIB He isotopic signature, plume buoyancy flux and overlying plate velocity. In this interpretation, the MORB-like 3He/4He (8 ± 1 Ra) at Fogo reflects a combination of (i) low to medium magma productivity, (ii) relatively low plume buoyancy flux (∼1.1 Mg/s), and (iii) slow average velocity (∼3 cm/yr) of the overlying plate.

High-precision analysis of carbon isotopic composition for individual CO2 inclusions via Raman spectroscopy: Addressing issues arising from the laser-heating effects

The carbon isotopic composition of carbon dioxide fluid inclusions trapped within minerals reflects the origin and evolution of the CO2-bearing fluids and melts. Recently, we developed a highly accurate method using Raman spectroscopy to determine the carbon isotopic composition of CO2 fluid inclusions, by simultaneously collecting 13CO2 and hot bands at a controlled temperature, and using the peak height ratio of 13CO2 and one of hot bands near 1410 cm−1 (HR) to determine δ13C value. This microanalytical technique enables precise measurements of the δ13C values of different CO2 fluid inclusions within zoned mineral crystals to reveal the multiple-stages evolution of CO2-bearing fluids and melts. However, when studying fluid inclusions hosted within high laser heating coefficient minerals such as olivine and pyroxene in mantle xenoliths, local temperature near the inclusions will be higher than the temperature controlled by heating-cooling stage. To address this issue, we examined the effects of laser heating on CO2 isotopic standard samples sealed in the silica capillary, and developed a novel procedure to determine the δ13C values of natural fluid inclusions by using two CO2 standard samples with known carbon isotopic compositions. The proposed workflow successfully determines the δ13C values of natural CO2 inclusions, with an average deviation of 0.58 ‰ between the measurements and the model.

Geochemical evidence for a lithospheric origin of the Comoros Archipelago (Indian Ocean) as revealed by ultramafic mantle xenoliths from La Grille volcano

Petrology and fluid inclusions (FI) geochemistry are increasingly used in tandem to constrain the compositional features and evolution of the lithospheric mantle. In this study, we combine petrography and mineral chemistry with analyses of noble gases (He, Ne and Ar) and CO2 in olivine, orthopyroxene- and clinopyroxene-hosted FI, as well as radiogenic isotope (Sr-Nd-Pb) systematics of ultramafic xenoliths collected at La Grille volcano in Grande Comore Island, aiming at better characterizing one of the most enigmatic and controversial portions of the western Indian Ocean lithospheric mantle. Xenoliths have been divided in three groups on the basis of their textural features: Group 1 (Opx-bearing), Group 2 (Opx-free) and Group 3 (Cumulate). Overall, petrographic observations and mineral phase compositions indicate that the sampled lithospheric portion experienced variable degrees of melting (from 5% to 35%), recorded by Group 1 most refractory harzburgites and lherzolites, as well as modal metasomatic processes as evidenced by the crystallization of cpx at the expense of opx in Group 1 fertile lherzolites and wehrlite and by Group 2 xenoliths. Crystallization of slightly oversaturated basic silicate melts seems also to have occurred, as shown by Group 3 xenoliths. A positive trend between temperature and ƒO2 is evident, with Group 2 and 3 xenoliths testifying for hotter and more oxidised conditions than Group 1. The variability of the 4He/40Ar* ratio (0.02–0.39) in Group 1, significantly below typical values of a fertile mantle (4He/40Ar* = 1–5), can be explained by the variable degrees of partial melting coupled to metasomatic enrichment that may account for modifying 4He/40Ar*, as also indicated by the mineral composition. He-Ar-CO2 relationships support the presence of a metasomatic CO2-rich process post-dating the melt extraction and the cumulate formation. The air-corrected 3He/4He isotopic ratios (6.30 to 7.36 Ra) are intermediate between the MORB mantle signature (8 ± 1Ra) and the SCLM (6.1 ± 0.9 Ra). The Ne and Ar isotopic signatures (20Ne/22Ne, 21/Ne/22Ne and 40Ar/36Ar) are consistent with mixing between an air-derived component and a MORB-like mantle, supporting the hypothesis for a lithospheric origin of the Comoros magmas, and arguing against any deep mantle plume-related contribution. This is also corroborated by combining Ne with He isotopes, showing that La Grille ultramafic xenoliths are far from the typical plume-type compositions. Sr-Nd-Pb isotope systematics in opx and cpx from La Grille additionally support a MORB-type signature for the lithospheric mantle beneath the area.

Spatially resolved CO2 carbon stable isotope analyses at the microscale using Raman spectroscopy

Measuring the carbon stable isotope ratio (13C/12C, expressed as δ13CCO2) in geogenic CO2 fluids is a crucial geochemical tool for studying Earth's degassing. Carbon stable isotope analysis is traditionally performed by bulk mass spectrometry. Although Raman spectroscopy distinguishes 12CO2 and 13CO2 isotopologue bands in spectra, using this technique to determine CO2 isotopic signature has been challenging. Here, we report on in-situ non-destructive analyses of the C stable isotopic composition of CO2, applying a novel high-resolution Raman configuration on 42 high-density CO2 fluid inclusions in mantle rocks from the Lake Tana region (Ethiopia) and El Hierro (Canary Islands). We collected two sets of three spectra with different acquisition times at high spectral resolution in each fluid inclusion. Among the 84 sets of spectra, 58 were characterised by integrated 13CO2/12CO2 band area ratios with reproducibility better than 4‰. Our results demonstrate the determination of δ13CCO2 by Raman spectroscopy in individual fluid inclusions with an error better than 2.5 ‰, which satisfactorily matches bulk mass spectrometry analyses in the same rock samples, supporting the accuracy of the measurements. We thus show that Raman Spectroscopy can provide a fundamental methodology for non-destructive, site-specific, and spatially resolved carbon isotope labelling at the microscale.

In situ Raman spectroscopic measurement of the 13C/12C ratio in CO2: Experimental calibrations on the effects of fluid pressure, temperature and composition

The carbon isotope (δ13C) signature of CO2 within fluid inclusions is of significance to investigate because it can be used to decipher the carbon source of geological fluids. Raman spectroscopy has been applied to determine the δ13C of pure CO2. However, whether this approach can be applied to natural inclusions with complex compositions remains unknown. Here we present Raman spectra of CO2 ± N2 ± CH4 systems with known 13C/12C ratio (0.01–1.12) at temperatures (T) of 21 °C and 40 °C and at pressures (P) ranging from 0.5 to 50 MPa. Peak areas and peak heights of the 13CO2 (∼1370 cm−1) and 12CO2 (∼1285 cm−1) bands were determined to calculate the Raman spectroscopic quantification factors (F- and G-factor ratio). The results show that the quantification factors vary significantly with rising pressure in the low pressure range (e.g., <10 MPa), especially for pure CO2 system. Different fluid systems are characterized by pressure dependences. Specifically, both F- and G-factor ratios for CO2 fluid with a low 13C/12C ratio (e.g., 0.01) are different from that with a high 13C/12C ratio (e.g., 0.13) under the same T-P conditions. Fluid temperature does not result in significant variation in F- or G-factor ratios at the investigated temperatures. Based on these calibrations, we suggest that fluid pressure and composition (x) are prerequisites for Raman spectroscopic measurements of the 13C/12C ratio of CO2. However, the 13CO2 (∼1370 cm−1) band for CO2 from natural fluid inclusions is characterized by low Raman intensity, resulting in large errors in calculated peak area and peak height. Thus, accurate determination of the 13C/12C ratio of fluid inclusion CO2 is not feasible for inclusions with low CO2 density. Nevertheless, this method can be applied to investigate the carbon isotope fractionation in 13C labelled hydrothermal experiments, where CO2 with high a 13C/12C ratio is produced.

Ore Genesis of the Toudaochuan Gold Deposit in Central Jilin Province, NE China: Constraints from Fluid Inclusions and C–H–O–S–Pb Isotopes

The Toudaochuan gold deposit is a recently discovered lode gold deposit in Central Jilin Province. Gold ore bodies are dominantly controlled by NE-trending fault. The major hydrothermal period can be further divided into the quartz–pyrite stage (stage I), quartz–gold–polymetallic sulfides stage (stage II, major gold mineralization stage), and quartz–carbonate stage (stage III). Primary fluid inclusions (FIs) identified in quartz at different hydrothermal stages include liquid-rich aqueous FIs (L-type), CO2 FIs (C-type, including CO2-bearing C1-type FIs and CO2-rich C2-type FIs), and minor vapor-rich aqueous FIs (V-type). Microthermometry studies on different fluid inclusions indicate that the original ore-forming fluids belonged to the CO2–H2O–NaCl system characterized by a moderate–low temperature and low salinity in stages I and II, and they finally evolved into a H2O–NaCl system characterized by low temperature and low salinity in stage III. Fluid immiscibility is considered to be the key ore-forming mechanism. The initial ore-forming fluid was originated from magmatic water and was mixed with meteoric water in the later stage. The S and Pb isotope data suggest that the ore metal materials were derived from the mixed source of mantle and crust. Based on all the above data, therefore, it can be proposed that the Toudaochuan gold deposit is a mesothermal magmatic–hydrothermal gold deposit.

Fluid Inclusions and Stable Isotope Geochemistry of Gold Mineralization Associated with Fine-Grained Granite: A Case Study of the Xiawolong Gold Deposit, Jiaodong Peninsula, China

The Xiawolong gold deposit, located in the Muping–Rushan gold metallogenic belt (eastern Jiaodong Peninsula), is a newly discovered deposit that developed in the late Early Cretaceous as fine-grained granite. Gold mineralization, which mainly occurs in the middle of fresh fine-grained granite dikes, consists of stockwork-style and disseminated ores. They are characterized by middle-high-temperature mineral assemblages, such as molybdenite and magnetite, associated with gold-bearing pyrite. Four types of primary fluid inclusions, contained within the quartz grains from the gold-bearing disseminated and stockwork-style fine-grained granitic ores, were identified based on microthermometry and Raman spectroscopy. The types identified were type 1 aqueous inclusions with middle-high temperature (201 to 480 °C) and middle-low salinity of 0.18 to 17.00 wt.% NaCl equiv.; type 2 H2O–CO2 inclusions, which show middle-high temperatures (218 to 385 °C), middle-low salinities (1.23 to 13.26 wt.% equiv. NaCl), and variable XCO2 (0.031 to 0.044); type 3 daughter mineral-bearing inclusions with high temperature (416 to 446 °C) and relatively constant and high salinity (28.59 to 32.87 wt.% NaCl equiv.); and type 4 CO2 fluid inclusions, which possess a bulk density of 0.405 to 0.758 g/cm3 and a constant XCO2 (0.952 to 0.990) (according to the decreasing abundance of fluid inclusions). The δ18Owater range is between 3.4 and 5.9‰, and the range of the δD is from −97.1 to −77.4‰, which indicates that the ore-forming process is of a magmatic water origin. The δ34S values possess a narrow range between 4.5 and 9.3‰, indicating the source of the Mesozoic Kunyushan granitoids. The Pb isotopic compositions of pyrite show that the Mesozoic Kunyushan granitoids are the main lead source for pyrites. Types 1, 2, and 3 fluid inclusions coexist in the same view field of the quartz grain, which are suggested to occur as the result of fluid immiscibility because of the boiling of a single homogeneous NaCl-CaCl2-KCl-CO2-H2O system. The fluid immiscibility, rather the fluid mixing and wall-rock sulfidation, is the mechanism of gold precipitation in the Xiawolong deposit. Compared with both the “Linglong-type” and “Jiaojia-type” gold deposits in the Jiaodong Peninsula in terms of geological–petrographic evidence and all of the available geochemical data, it can be concluded the Xiawolong gold deposit is of magmatic hydrothermal origin, having a genetic relation to the fine-grained granite.

Origin of pegmatitic melts from granitic magmas in the formation of the Jiajika lithium deposit in the eastern Tibetan Plateau

Granitic pegmatites may be genetically related to granites. However, it is still debatable how pegmatitic melts originated from granitic magmas. For example, a possible mechanism of melt–melt immiscibility for the origin of pegmatitic melt has not been well documented. The Jiajika Li deposit in the eastern Tibetan Plateau is a world-class deposit and is hosted in pegmatites, which occurred as dikes surrounding their source granite (two-mica granite). This paper concerns melt inclusions (MIs) in quartz from the granite–marginal pegmatite (GMP) at the roofward contact of the two-mica granite with the country-rock schist, as the MIs from such pegmatite are considered to represent the original pegmatitic melt and hence are ideal for investigating the origin of pegmatitic melts from granitic magmas. The MIs can be classified into H2O–CH4- and H2O–CO2-bearing types, both containing solid phases, including muscovite, albite, and apatite; the H2O–CO2-bearing MIs are usually associated with the H2O–CO2 fluid inclusions. To prevent leakage or decrepitation of these MIs during heating, external pressures were applied by using a hydrothermal diamond-anvil cell. The compositions of muscovite inside the unheated MIs and glass inside the MIs, which was quenched from a homogenous state, were analyzed using electron microprobe analysis (EMPA) and laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS). During heating, the H2O–CH4-bearing MIs were homogenized into an H2O-saturated melt mostly at 750–800 °C, while the H2O–CO2-bearing MIs, when similarly treated, showed H2O–CO2-oversaturated entrapment features. The H2O–CH4-bearing MIs are considered to be trapped from the original pegmatitic melt containing ∼12 wt% H2O with up to ∼1000 ppm Li, ∼1500 ppm Rb, and ∼1800 ppm Cs, at pressures of ∼550–700 MPa. Based on previous MI-homogenization experiments, it has been reported that the microthermometry features and compositions (e.g., H2O contents) of the H2O–CH4-bearing MIs in the GMP quartz are similar to those in an H2O-rich melt, which was immiscible with an H2O-poor melt inside the heated MIs in quartz from the two-mica granite. Accordingly, in this study, we demonstrate that pegmatitic melts could be originated via melt–melt immiscibility of granitic magma, and that the initial exsolution of the pegmatitic melt from granitic magma can occur on a very small scale, as tiny droplets whose sizes may be similar to those of the observed MIs in granite. In addition to the enrichment of Li, B, and P, the enhanced H2O content under low oxygen fugacity condition in the granitic magma, as well as the decrease in pressure following the magma emplacement, could promote the melt–melt immiscibility.

Fluid Inclusion and Titanite U-Pb Age Constraints on the Yuanjiang Ruby Mineralization in the Ailao Shan-Red River Metamorphic Belt, Southwest China

ABSTRACT The Yuanjiang marble-hosted ruby deposit lies in the central segment of the Ailao Shan metamorphic massif of the Ailao Shan-Red River metamorphic belt. The mineralizing fluid and age were characterized by detailed petrography, Raman spectroscopy, microthermometry, and in situ titanite laser ablation-inductively coupled plasma-mass spectrometry dating. Some fluid inclusions in the corundum show an interesting morphology with a diaspore crystal fully separating the whole inclusion into two smaller inclusions. This morphological feature can be explained by morphological ripening and subsequent reactions between the trapped H2O and the host corundum during the cooling of the inclusion. Fluid inclusions in the ruby belong to the system CO2–H2S–COS–S8–H2S2–CH4–AlO(OH) with various daughter minerals, including diaspore, gibbsite, and native sulfur (S8). The observed seven-component fluid inclusion composition can be explained by two steps: (1) original fluid inclusion capture during deposit formation with compositions including CO2, H2S, COS, CH4, S8, and H2S2, and (2) post-entrapment fluid inclusion modification, such as diaspore and gibbsite. The presence of hydrous minerals in fluid inclusions strongly supports the idea that water was once present in the initial fluids. In the Yuanjiang deposit, petrographic evidence shows that titanite formed simultaneously with ruby, and U-Pb dating of titanite allows us to conclude that the ruby mineralization formed at 23.4 ± 0.3 Ma, in other words during the Himalayan orogeny.

THERMOBAROGEOCHEMICAL EXPLORATION AND ASSESSMENT CRITERIA OF GOLD MINERALIZATION OF THE BALKA SHYROKA DEPOSIT (MIDDLE DNIEPER REGION)

A scheme of the staging and thermobaric regime of the formation of the Balka Shyroka deposit gold mineralization (Middle Dnieper megablock of the Ukrainian Shield) was constructed, and the sequence and thermobaric intervals of ore formation were determined. Mineral paragenesises are combined into four mineral associations that form a series of mineral complexes: pre-productive magnetite-quartz, productive polysulphide, which includes two productive gold-bearing associations (arsenopyrite-pyrite-quartz with gold and gold-sulphosalt) and post-productive carbonate (quartz-calcite mineral association). Gold-producing associations were formed in a rather narrow range of temperature and pressure changes of the ore-forming environment specific to its composition and aggregate-density state. This affected the phase typomorphism of the respective families of fluid inclusions. Carbon dioxide-water inclusions with different phase ratios are common: Г—РСО2—РН2О, РСО2—Г—РН2О, РСО2—РН2О, Г—РСО2. The most optimal temperature for homogenization of gas-liquid inclusions (according to the first type) is 210-290 °С. In minerals, there are families of two-phase and one-phase CO2 fluid inclusions with wide variations in its density (from 0.65 to 0.87 g/cm3) and homogenization into the liquid phase. These typomorphic features are thermobarogeochemical search criteria and evaluation signs of gold mineralization. Equally important is the definition of the paleotemperature gradient and the spatial extrapolation of its change with depth, which makes it possible to calculate the vertical extent of mineralization, the level of its erosional section, and the depth of thinning out.

Carbon and oxygen isotopic composition of fluid inclusion CO2 and CH4 within the Archean Junction gold deposit, Kambalda, Western Australia

ABSTRACT The Junction orogenic gold deposit in the St Ives district of Western Australia is characterized by a syn-gold mineral assemblage dominated by quartz-calcite-albite-biotite-chlorite-pyrrhotite. The deposit had a light hydrocarbon,CO2, and O2 soil-gas signature above known mineralization prior to mining and it has been proposed that the source of the light hydrocarbon gases in the soil was gas-rich fluid inclusions trapped in gold-related alteration minerals, particularly calcite, albite, quartz, and pyrrhotite. Linking the soil gases with those in the deposit is extremely difficult. However, establishing that the gases in the soil are indeed present within the deposit and that those gases are related to the syn-Au alteration minerals is achievable through stable-isotope studies. Carbon and O stable-isotope compositions of pre-gold, syn-gold, and post-gold quartz veins; syn-gold and post-gold calcite; and CO2 and CH4 in the fluid inclusions that each of these minerals host were investigated to establish if the various mineral and fluid-gas species in the deposit are in isotopic equilibrium with each other, an important first step to relate syn-ore minerals with the relevant gases. Pre-ore Mo-type quartz veins contain CO2 (δ13Cgas = –1‰) and CH4 (δ13Cgas = ca. –33‰) in fluid inclusions at a ratio of ca. 93:7. The paucity of Mo-type quartz veins in the deposit suggests that these veins were not the main source of the soil-gas signature. Syn-gold alteration post-dates the Mo-type quartz veins. Quartz and co-existing calcite in the Au-bearing Junction shear zone have δ18Omineral values around 12.0 and 10.5‰, respectively. Multiple co-existing quartz-calcite pairs indicate that gold deposition occurred at ∼400 °C. This temperature agrees with mineral equilibria temperature estimates, the entrapment temperatures of fluid inclusions, and temperature modelling of solid-solution mineral phases. The temperature dictates that the quartz and calcite are in isotopic equilibrium with each other. The calcite in the Junction shear zone has δ13Cmineral values from –7.4 to –2.5‰, indicating that the CO2-rich ore fluid had a δ13Cfluid value of –3.7 ± 0.9‰. CO2 and CH4 released from quartz-hosted fluid inclusions have δ13Cgas values from –4.3 to +3.5‰ (mean = –1.5 ± 1.9‰) and –50.5 to –35.2‰, respectively. The isotopic composition of the fluid inclusion CO2 is in disequilibrium with co-existing CH4 that was co-released from the same quartz vein and the calculated δ13Cfluid value from co-existing calcite. Isotopic mass balance calculations using the two co-released gases show that the CO2 was initially in equilibrium with the syn-ore calcite but has since re-equilibrated with CH4 at temperatures below 200 °C. The abundance of CH4 in some quartz veins suggests that the syn-gold vein assemblage could be the source for the soil-gas anomaly. Post-gold veins contain quartz and calcite that have δ18Omineral values of ca. 11.0 and 10.0‰, respectively. Individual mineral pairs indicate precipitation at ∼320 °C from a fluid with a δ18Ofluid value of 4.7 ± 0.9‰, distinct from that which formed the syn-gold quartz veins. The post-gold calcite has δ13Ccalcite values from –7.5 to –5.4‰, indicative of formation from a CO2-bearing fluid having a δ13Cfluid value of –4.6 ± 0.9‰. The δ13Cfluid values are indistinguishable from fluid inclusion CO2 values of –3.6 ± 0.9‰, indicating no post entrapment re-equilibration, which suggests that CH4 was at trace volumes or absent in the post-gold quartz veins. These data lead to the conclusion that post-entrapment reequilibration between fluid inclusion CO2 and CH4 has occurred, but that the two gases were likely in equilibrium at the time of entrapment. This has implications for the interpretation of C isotope studies that focus on fluid inclusion CO2 measured from other gold and base-metal deposits, especially when the isotopic value of that CO2 is assumed to represent a specific source for the ore-forming fluids. The data also lead to a model that proposes that the syn-gold alteration assemblage could have produced the soil-gas anomalies observed above the mineralization.

Recycled crustal carbon in the depleted mantle source of El Hierro volcano, Canary Islands

The Canary Islands, in the eastern Atlantic, are among the most enigmatic Oceanic Island provinces on Earth, as the mantle source feeding its volcanism exhibits wide spatial heterogeneity and a multiplicity of sources. Multi-isotope whole-rock studies have long revealed the presence of a recycled oceanic crust/lithosphere component in the mantle source. However, noble gas systematics have been more challenging to interpret, and the available carbon isotope data is limited and cannot support/dismiss this interpretation. Here, we present the very first isotopic characterisation of CO2 and noble gases (He-Ne-Ar) in fluid inclusions (FI) in minerals hosted in mantle xenoliths from El Hierro, the youngest and westernmost island of the Canary volcanic archipelago. Six fresh xenoliths from El Julan cliff valley were analysed (3 spinel lherzolites and 3 spinel harzburgites). We find carbon isotopic compositions of CO2 in FI (δ13C) ranging from −2.38 to −1.23‰ in pyroxenes and from −0.19 to +0.96‰ in olivines. These unusually positive δ13C values, well above the typical mantle range (−8‰ < δ13C < −4‰), prove, for the first time, the presence of a recycled crustal carbon component in the local source mantle. We interpret this 13C-rich component as inherited from a mantle metasomatism event driven by fluids carrying carbon from C. In contrast, our El Hierro xenoliths identify a depleted mantle-like He signature, with an average Rc/Ra ratio (3He/4He normalised to air ratio and corrected for atmospheric contamination) of 7.45 ± 0.26 Ra. The involvement of depleted mantle-like fluids, variably admixed with air-derived components (possibly recycled via paleo-subduction event(s)), is corroborated by Ne-Ar isotopic compositions. The depleted mantle-like He signature suggests instead the involvement of a primordial He source in the local lithospheric mantle and indicates a marginal role played by past subduction events in modifying the local mantle He budget. When put in the context of previous 3He/4He measurements in FI and surface gases along the Canary archipelago, our results confirm an overall west-to-east decrease of Rc/Ra ratios, which may be interpreted as due to increasing contributions from the African sub-continental mantle, the addition of radiogenic 4He during magma migration in the oceanic crust (whose thickness increases eastward) and/or magma ageing.

Spectroscopy and Microscopy of Corundum from Primary Deposits Found in Greece

Corundum primary deposits in Greece occur in four locations: Paranesti in Drama and Gorgona in Xanthi, both belonging to the wider Rhodope Massif, as well as, Ikaria island and Kinidaros in Naxos island, both belonging to Attic-Cycladic Massif. Eight samples were examined with spectroscopic methods (FTIR, UV-Vis, EDXRF) in order to better characterize these four primary deposits: two pink sapphires from Paranesti, a pink and a blue sapphire from Gorgona, two blue sapphires from Ikaria and three blue sapphires from Kinidaros. Under the microscope, all samples present characteristics linked to post-crystallization deformation, decreasing their gem quality. The FTIR absorption spectra of all samples present in different relative intensities, bands of boehmite, diaspore, goethite, mica and/or chlorite inclusions and CO2 in fluid inclusions. Boehmite and diaspore inclusions are most likely epigenetic. In the UV-Vis spectra, the pink color of the samples is linked with Cr3+ absorptions and the blue color with absorptions due to Fe2+-Ti4+ intervalence charge transfer. EDXRF analyses in the studied samples show relatively high titanium and iron concentrations that are related with mineral inclusions. Gallium is slightly variable in samples from different regions; also, different colored samples from Gorgona present diverse gallium content.

Features of Mineral Crystallization at Different Stages of the Magmatism Evolution of the Gorely Volcano (Kamchatka): Data on Melt and Fluid Inclusions

Abstract ––Studies of melt and fluid inclusions and minerals as well as computational modeling (based on the data on the composition of melt inclusions, clinopyroxenes, and amphiboles) gave an insight into the physicochemical parameters of magmatic systems during the evolution of the precaldera Pra-Gorely Volcano and during the subsequent formation of rock complexes of the Young Gorely Volcano. The estimated temperatures of crystallization of olivine, clinopyroxene, and plagioclase phenocrysts (1115–1260 °С) and amphibole (740–890 °С) are in agreement with the earlier published data on the magmatism of the Gorely Volcano. Computational modeling based on the compositions and homogenization temperatures of melt inclusions showed that the established depth interval of mineral crystallization (21.0–1.5 km) with pressures of 7.0–0.5 kbar can be divided into two ranges, 21–15 km and 9.0–1.5 km. Both the Pra-Gorely and Young Gorely volcanoes have magma chambers in these depth ranges. The Pra-Gorely Volcano is characterized by higher temperatures of mineral crystallization (1240–1190 °С) as compared with the Young Gorely Volcano (1190–1125 °С). The presence of primary fluid inclusions with low-density CO2 and of syngenetic primary melt inclusions in plagioclase of the Pra-Gorely Volcano indicates that the mineral crystallized from a heterophase melt. At the same time, the cores of plagioclase phenocrysts formed from a homogeneous melt. A drastic drop in pressure led to the phase separation of magma throughout the magma column (upper and lower chambers) and to the growth of zones saturated with CO2 fluid inclusions in the plagioclase crystals formed from a two-phase melt. The subsequent closure of the system and the disappearance of CO2 phase resulted in the growth of plagioclase from a homogeneous melt.

High $${f_{{{\rm{H}}_2} - }}{f_{{{\rm{S}}_2}}}$$ Conditions Associated with Sphalerite in Latala Epithermal Base and Precious Metal Deposit, Central Iran: Implications for the Composition and Genesis Conditions of Sphalerite

This paper presents the properties of fluid inclusions found in sphalerite from Latala epithermal base and precious metal deposit (Central Iran), which is hosted in Cenozoic volcanic-sedimentary host-rocks. The Latala Deposit represents an example of vein type, base metal deposits in the Miduk porphyry copper deposits (PCDs) in southern Urumieh-Dokhtar magmatic belt (UDMB). Mineralization in Latala epithermal base and precious metal vein type formed in 3 stages and sphalerite-quartz veins occur in stages 2 and 3. Stage 2 quartz-sphalerite veins are associated with chalcopyrite and zoned sphalerite, along with quartz+hematite, and Stage 3 quartz-sphalerite veins contain galena+sphalerite+ chalcopyrite and quartz with overgrowth of calcite. Mineralization in Stage 3 occurs as replacement bodies and contains Fe-poor sphalerite without zoning in the outer parts of the deposit. This paper focuses on fluid inclusions in veins bearing sphalerite and quartz. The fluid inclusion homogenization temperatures and salinity in sphalerite (some with typical zoning) range from 144 to 285 °C and from 0.2 wt.% to 7.6 wt.% NaCl eq. Sphalerite and fluid inclusions of the Latala base and precious metal deposit formed from relatively low-T and low-salinity solutions. Raman spectroscopy analyses indicate a high percentage of CO2 in the gas phase of fluid inclusions in Fe-poor sphalerites, as expected with melting temperature for CO2 of −56.6 °C, and significant amounts of H2. Lack of reduced carbon species (methane and lighter hydrocarbons) was confirmed in the petrographic study using UV light and Raman spectroscopy. High amounts of H2 in fluid inclusions of Fe-poor sphalerite can be the result of different intensities of alteration and diffusion processes. The common occurrences of CO2 in fluid inclusions have originated from magma degassing and dissolution of carbonates. The δ34S values for sulfide minerals in galena of sphalerite bearing veins vary between −9.8‰ and −1.0‰, and the δ34S values calculated for H2S are between −7.1‰ and +0.6‰. These values correspond to magmatic sulfur whit possible interaction with wall rocks. Magmatic fluids were successively diluted during cooling and continuous ascent. Secondary boiling would lead to variable amounts of potassic or prophylactic alteration and the hydrogen diffusion into the inclusions hosted in sphalerite of Latala.

Pressure measurement and detection of small H2O amounts in high‐pressure H2O–CO2 fluid up to 141 MPa using Fermi diad splits and bandwidths of CO2

AbstractDependence of residual pressures of fluid inclusions on their size and host mineral species provides valuable information related to the depth provenance and P–T–t path of the rocks. Although Raman‐based barometry is an effective method for ascertaining the internal pressure of H2O–CO2 fluid inclusions, few studies have elucidated Raman spectral features of CO2 in a system of high‐pressure H2O–CO2. New experiments using a high‐pressure optical cell in this binary system with compositions of 100, 75 ± 2, and 60 ± 2 mol% CO2 were conducted for this study to verify the availability of Raman CO2 barometers for use in assessing the temperature and pressure conditions of approximately 22°C and 17.3–141.4 MPa. Our results demonstrate that the existence of H2O does not affect the relation between Fermi diad splits (Δ, cm−1) and total pressure of pure CO2. These results suggest that the Δ–total pressure relation obtained from pure CO2 is also applicable to H2O–CO2 systems, even at high pressure. However, unlike Δ, because the peak positions of the Fermi diad in the system of H2O–CO2 shift to a higher wavenumber than those of pure CO2 at given pressure higher than 30 MPa, the peak positions are not very suitable for the pressure scale in an H2O–CO2 system. Additionally, we confirmed the availability of bandwidths of CO2 as an indicator of compositions that can identify the presence of very small amounts of H2O (at least 0.3 mol% H2O), even at room temperature.

Primary CO2-bearing fluid inclusions in granulitic garnet usually do not survive

CO2-bearing fluid inclusions (FI) from granulites have been the main advocate for an active role of fluids during high-temperature metamorphism, yet the fluid regime of the deep crust and the role of fluids remain largely debated topics. In this dispute, one of the most controversial issues is the timing of FI entrapment relative to peak metamorphic conditions. Here we investigate three world-renowned high- to ultra-high temperature metamorphic terranes to evaluate the fate of primary CO2 and COH fluid inclusions certainly trapped during the prograde path. Fluid inclusions coexist along with nanogranitoids in peritectic garnet. Combination of cutting-edge techniques indicates that the FI are composed of fluid and aggregates of solid phases. The latter usually comprises siderite, ferroan magnesite, pyrophyllite, calcite, corundum, quartz, and in some cases kaolinite, dolomite, biotite and muscovite. In the fluid phase, low-density CO2 is the most common component and no free H2O has been detected. Methane and N2 may be also present. The high proportion of solids in the FI with carbonates and OH-bearing phases cannot have precipitated as daughter phases directly from a simple COH-fluid as daughter phases. These minerals require additional cations (e.g. Fe, Mg, Ca, Al, Si) which may be dissolved in very small amounts in crustal fluids and yet are very abundant in the host. The solids, therefore, imply that the initial composition of high-density carbonic inclusions must have been changed by the interaction with the host garnet during cooling. Thermodynamic modelling of such fluid-garnet interaction demonstrates that the assemblages found in FI are metastable and that, whatever retrograde path is followed by the host rock, primary C-bearing FI must change their nature to a multiphase assemblage of stepdaughter minerals as a natural consequence of cooling. It follows that supposed primary unmodified FI in garnet previously reported in the literature are, in most cases, secondary, retrograde features whose low temperature of entrapment inhibited fluid-host interaction. Our finding undermines the main pillar of the theory of carbonic fluid-assisted metamorphism (the presence of superdense CO2 inclusions in granulites), but at the same time it offers a novel perspective to identify prograde COH fluids in the deep hot crust.

Neogene Metasomatism in the Subcontinental Lithosphere beneath SE Asia—Evidence from Modal and Cryptic Phosphorus Enrichment in Peridotites and Pyroxenites from Southern Laos

AbstractMetasomatism is the prime process to create compositional heterogeneity of the upper mantle. Mineralogical and mineral chemical changes of the mantle triggered by metasomatism can be used to deduce the nature of the metasomatic agent(s) and to constrain the timing of metasomatism. This information is vital for an understanding of the secular evolution of a given mantle segment and the magmatic processes occurring therein. For this study spinel-lherzolites and -websterites were collected from ∼16 Myr old alkali-basaltic lava flows that were extruded on the Bolaven Plateau in south–central Laos. These xenoliths are fragments of the shallow continental lithosphere of the SE Asian peninsula and originate from a mantle segment that acted as source for Cenozoic basaltic volcanism in the wake of the India–Asia collision. In both rock types modal metasomatism formed apatite ± whitlockite ± phlogopite ± calcic amphibole ± calcite ± orthopyroxene. The principal metasomatic phase is apatite, which appears in three varieties. Type-I apatite is ±inclusion-free and associated with phlogopite, calcic amphibole, calcite and lamellar orthopyroxene. It is high in Na and low in P and shows low analytical totals indicating a type-B carbonate–apatite component. Type-I apatite presumably precipitated from a P-alkali-rich mixed H2O–CO2 fluid with low large ion lithophile element (LILE)–light rare earth element (LREE) contents. Type-II apatite shows a spongy texture and has lower Na and higher P contents with higher analytical totals. Crosscutting discontinuous zones of type-II characteristics within type-I apatites indicate type-II formation through an exchange Na+ + CO32– = PO43– + Ca2+ by a later fluid with lower aCO2. REE-rich type-III apatite is the youngest type and formed by infiltration of basaltic melts as part of spongy rims around clinopyroxene. One lherzolite contains whitlockite in addition to apatite. Whitlockite formation is ascribed to a short-lived metasomatic event involving a fluid with extremely low aH2O. Disequilibrium between whitlockite and the bulk assemblage is indicated by hydrous silicates in the immediate vicinity of whitlockite and by substantial H2O contents of 250–370 µg g–1 in clinopyroxenes and 170–190 µg g–1 in orthopyroxenes. High-density (1·15–≥1·17 g m–3) CO2–fluid inclusions in the whitlockite-bearing sample provide evidence for the presence of low-aH2O fluids at mantle depths. The spinel-herzolites may also show cryptic metasomatism evidenced by P zoning in olivine, which is characterized by P-poor (&amp;lt;20–130 µg g–1) cores and P-rich (170–507 µg g–1) rims, the latter in part with oscillatory zoning on a µm scale. Element correlations indicate [4]Si4+ + [6](Mg, Fe)2+ = [4]P5+ + [6]Li+, 2 [4]Si4+ + 4 [6](Mg, Fe)2+ = 2 [4]P5+ + 3 [6](Mg, Fe)2+ + [6]vac and/or 5 [4]Si4+ = 4 [4]P5+ + [4]vac as major P incorporation mechanisms. High P–T experiments conducted at 2 GPa and 950–1050 °C yield apatite-saturated P contents of olivine in the range ∼360–470 µg g–1. Most P concentrations in olivines from the xenoliths including those in the P-rich rims, however, are significantly lower than the apatite-saturated values, which indicates disequilibrium uptake of P during growth of the P-rich rims by dissolution–reprecipitation. Diffusion modeling indicates that the P zoning must have formed within decades prior to the eruption of the host basalts. This is consistent with the preservation of Li disequilibrium partitioning between olivine and pyroxenes in some of the xenoliths. All metasomatic phenomena were assigned to two metasomatic events, both of which were in close temporal relation with the eruption of the xenolith host basalts: an older event-1 formed type-I apatite, hydrous silicates, calcite and orthopyroxene and caused the modification of type-I apatite composition towards that of type-II. It is also likely to be responsible for whitlockite formation and P zoning in olivine. A younger event-2 comprises all paragenetic, textural and compositional modifications of the xenolith assemblages associated with the infiltration of basaltic melts.