Fluid Inclusions Research Articles

The interplay between dolomitizing fluids, tectonically-controlled saddle dolomite and calcite cements in lower Cambrian to Furongian strata in the Tazhong Uplift

The interplay between dolomitizing fluids, tectonically-controlled saddle dolomite and calcite cements in Lower-Cambrian to Furongian strata in the Tazhong Uplift, Tarim Basin were interpreted from petrography, geochemistry and fluid inclusions microthermometry. Stochiometric replacement dolomites (RD1, RD2 and RD3) and saddle dolomite (DC) cement were identified. Equant-drusy calcite (ECAL) and blocky-to columnar calcite (LCAL) cements were identified. Weak relationships exist between δ13C, δ18O, 87Sr/86Sr, Mg/Ca versus Mn/Sr ratios, which are tools used to evaluate the impact of diagenetic environment on C–O–Sr isotope composition of the carbonates. The replacement dolomites and DC with high Mg/Ca ratios (0.97–1.21) have low depleted δ18O, δ13C values, compared to the ECAL and LCAL with more depleted δ18O, δ13C values, indicating that the C–O–Sr isotope composition suffered diagenetic alteration by higher-temperature and equilibrium isotopic fractionation. The carbonates fluid system is characterized by negative shift in C–O-isotopic composition with hypersaline signatures compared to Early Paleozoic evaporative seawater. Moreover, the increasing trend in (Cl, Br, I)/(CaO + MgO) ratios with Mg/Ca ratios, couple with positive relationship between Cl and Br, suggests fluids contamination by halogen-rich inclusions. The RD1, RD2 and RD3 were precipitated by relatively higher-temperature saline fluids at depth during shallow-deep burial dolomitization. The DC have average Th-values (141.5–199.2 °C) mostly higher than the estimated ambient temperatures (165 °C) of the studied strata, meaning their growth in fractures resulted from higher-temperature Mg-enriched saline basinal fluids conveyed by hydrothermal convection and short-lived geothermal squeegee-type flow. The LCAL were precipitated by Ca/Mg-enriched basinal brine fluids diluted by influx of meteoric water, cementing fractures in host rocks, as dolomite was replaced by calcite (i.e., calcitization). The conceptual model reveals that dolomitizing fluids and calcitization fluids were conveyed through permeable horizons resulting from strong extensional tectonics and weak compressional tectonics, forming irregular networks of saddle dolomite and calcite cement in host rocks.

Formation mechanism of carbonate cement in tight sandstone reservoirs in the depression zone of foreland basin and its impact on reservoir heterogeneity: The upper Triassic Xujiahe Formation in Western Sichuan foreland basin, China

The carbonate cements in tight sandstone reservoirs are diverse, complex, and important determinants of reservoir quality. This study provides a comprehensive analysis of the characteristics and formation mechanism of carbonate cement in the tight sandstone reservoirs of the Xu3 Member within the Xujiahe Formation in the depression zone of the Western Sichuan foreland basin. Core samples were examined on thin sections using cathodoluminescence and scanning electron microscopy, fluid inclusion analysis, in situ carbon and oxygen stable isotopes, and rare earth element analysis. The study reveals that the Xu3 Member primarily comprises sublitharenite and litharenite, which has three stages of carbonate cementation within the reservoirs. On average, the reservoirs exhibit a porosity of 3.82% and a permeability of 0.1mD. In the eodiagenetic stage, calcite and dolomite (δ13CPDB = 0‰ to −4.07‰; δ18OPDB = −5.64‰ to −12.69‰) formed, filling both intergranular pores and intragranular dissolution pores. This process is driven by the expulsion of organic acids through compaction from the clay and coal-bearing sections during shallow burial. The carbon sources originate from external organic acids and internal carbonate rock fragments, which combine with Ca2+ and Mg2+ ions released from the dissolution of carbonate rock fragments. During the mesodiagenetic stage A, the predominant formation of ferroan calcite and ankerite (δ13CPDB = −5.98‰ to −7.64‰; δ18OPDB = −14.47‰ to −19.87‰) occurred, filling intergranular residual pores and secondary intragranular dissolution pores. This phenomenon is caused by the expulsion of organic acids formed by the compaction of matured organic matter at greater burial depths. The carbon sources primarily originate from external organic acids and combine with Ca2+, Mg2+, and Fe2+ ions in the sandstone, alongside accompanying organic acids. During the mesodiagenetic stage B, coarse-macro crystalline calcites (δ13CPDB = −1.06‰ to −1.64‰; δ18OPDB = −17.95‰ to −20.36‰) with significant positive Eu anomaly-filled fractures were formed. These calcites are associated with hydrothermal fluids in the deep subsurface, precipitating directly in the fractures due to the presence of hot hydrothermal fluids rich in Ca2+ and CO32−. The Xu3 Member displays two sandstone superimposed types. In the mudstone overlain by sandstone type, carbonate cement is mainly present in the middle of the cycle, and reservoir quality is relatively high at both the bottom and top of the cycle. In the sandstone overlain by sandstone type, carbonate cement is predominantly found in the middle and top sections of the cycle, with higher-quality reservoirs primarily forming at the bottom of the cycle. It resulted in significant heterogeneity observed in the tight sandstone reservoirs of the depression zone in the Western Sichuan foreland basin.

Strontium Isotopic Variations of Authigenic Calcite in Clastic Strata Record Its Sediment Provenance and Fluid−Rock Interactions

Abstract Strontium isotopes of authigenic carbonate potentially record sediment provenance, fluid sources, and fluid–rock interactions, little was studied on this topic in clastic strata. This study investigated clastic rocks containing authigenic calcite in the Lower Triassic Baikouquan Formation in the Junggar Basin, northwestern China. Mineral compositional and fluid inclusion analyses were conducted to constrain the precipitation processes of authigenic calcite, and the Sr contents and isotope ratios of the calcite were also measured. The authigenic calcite was precipitated at 80–140°C as the final product of thermochemical oxidation of hydrocarbons and thus has high Mn contents and highly negative δ13CVPDB values (as low as −70‰). The calcite also exhibits anomalously low 87Sr/86Sr values (0.704827, 0.706612), which are lower than contemporaneous seawater and published 87Sr/86Sr values of carbonate cements in clastic sediments, and also much lower than 87Sr/86Sr values (0.722027, 0.736750) of alkali feldspar in the strata. These low 87Sr/86Sr values record the low 87Sr/86Sr of the dominant rocks in the provenance area, such as volcanic rocks. During diagenesis, especially mesodiagenesis, the charging of hydrocarbon-bearing fluids promoted abundant dissolution of orthoclase in the alkali feldspar detritus, releasing radiogenic 87Sr into the pore waters, and eventually increasing the 87Sr/86Sr values in the late-stage calcite that precipitated after this reaction. This inference is consistent with the positive correlation between the calcite 87Sr/86Sr ratios and the dissolution intensity of orthoclase. In regions that do not undergo hydrocarbon-charging and where orthoclase remains stable, the lower 87Sr/86Sr ratios of the calcite generally record the provenance. For authigenic calcite associated with intense fluid–rock interactions, the higher 87Sr/86Sr ratios reflect the enhanced dissolution intensity of 87Sr-rich minerals such as orthoclase. Therefore, combined with a petrological study, Sr isotopes of authigenic carbonate in clastic sediments can trace sediment provenance and intensity of fluid–rock interactions.

Dolomitization history and fluid evolution of end-ediacaran multi-phase dolomites from the near-surface to deep burial depths in the tarim craton, northwestern China

The deeply buried (>8 km) end-Ediacaran Qigebrak Formation dolostones in the Tarim Basin, China, have significant petroleum potential, but have experienced multi-stage dolomitization that has resulted in the occurrence of diverse dolomite phases. The features and origins of the different dolomite types were merely investigated, which hinders an in-depth understanding of the complex dolomitization processes. This paper presents an integrated petrological, geochemical (C–O–Sr isotope and in situ trace element), fluid inclusion microthermometric, and dolomite U–Pb dating study of outcrop and core samples, to investigate the dolomitization mechanisms, and the nature and evolution of the dolomitizing fluids. The results indicate the occurrence of early dolomitization triggered by seepage–reflux of mesosaline seawater, which retained the primary marine geochemical properties of most of the matrix dolomite. Subsequently, during early diagenesis, fibrous dolomite cement was precipitated from marine porewaters, which have similar geochemical characteristics to the matrix dolomites. Following this, during intermediate-depth burial diagenesis in the Ordovician, fine-to medium-crystalline dolomite cements formed at temperatures of 80–117 °C in association with dissolution–reprecipitation of the matrix and early fibrous cements or diagenetic interactions with clay minerals of the lower Cambrian Yurtus Formation shales. During deep burial diagenesis and dolomitization in the Carboniferous, coarse-crystalline dolomite cements formed at temperatures of 104–138 °C from saline brines enriched in middle rare earth elements. Saddle dolomites, formed by hydrothermal dolomitization (162–184 °C) that was closely related to Permian–Triassic volcanic activity, have positive Eu anomalies and depleted δ18O values, that resulted from the mixing of basinal brines with 87Sr-enriched hydrothermal fluids. This study provides a detailed description of multiple dolomitization events in deep time that affected deeply buried dolostones.

Decoupling of Cu and Zn in sediment-hosted base metal deposits: Evidence from LA-ICP-MS analyses of fluid inclusions and trace elements in minerals at Baiyangping, China

Copper and lead–zinc mineralization in basinal rocks worldwide commonly shows distinct spatiotemporal zonation. The Baiyangping deposit in the Lanping Basin, southwest China, is a large sediment-hosted polymetallic deposit that shows clear and pronounced zoning of Cu versus Pb-Zn mineralization. Here, we analyzed trace elements in pyrite and sphalerite and fluid inclusions in sphalerite, celestine, quartz, and dolomite to seek insights into the origins of the ore-forming fluids and the processes that govern the separation of Cu- from Zn-rich ores. We show that while the later Zn-rich mineralization is characterized by fluid inclusions showing typical hallmarks of basinal brine composition (low homogenization temperature < 230 °C, high salinity > 20 wt% NaCl eq., dominated by Na-K-Ca-Mg chlorides), the earlier Cu-rich mineralization shows markedly distinct composition that more closely resembles deeply-circulated water that has equilibrated with crystalline basement rocks (higher homogenization temperature of 210–280 °C, variable but lower salinity of ∼ 5–15 wt% NaCl, dominated by Na-K-Li chlorides). Pyrites formed during the earlier Cu-rich stage show elevated Cu, Co, Sb and Zn, while pyrites formed during the later Pb-Zn stage are more enriched in As, Pb and Mn. We interpret that the earlier-formed Cu-rich ores were deposited by deeply sourced fluids that ascended along basement-penetrating reverse faults, whereas the later Zn-rich ores were formed by subsequent circulation of fluid from within the basin, whose flux was promoted by shallower strike-slip faults. Hence, the two ore types reflect discrete pulses of chemically distinct hydrothermal fluids. We suggest that the evolving structural controls and fluid pathways during prolonged ore formation allowed sequential pulses of fluids that had acquired different metal budgets by equilibration with different sources. We suggest that this type of two-step process may be more common in sediment-hosted base metal deposits than single-fluid cooling sequential order of precipitation.

Geochemistry and accumulation of the ultra-deep Ordovician oils in the Shunbei oilfield, Tarim Basin: Coupling of reservoir secondary processes and filling events

Ultra-deep (7300 m–8900 m) condensed and volatile oil reservoirs have been discovered in the Ordovician reservoirs of the Shunbei oilfield, in the Tarim Basin. This study describes the petroleum accumulation process in the Shunbei oilfield by combining an analysis of its geochemical characteristics with seismic section observations and an analysis of petroleum filling events. Geochemical techniques are used to determine the sources, maturity, secondary processes, accumulation periods, and timing of petroleum filling. Analysis of fluid inclusion homogenization temperatures and burial-thermal histories indicates distinct petroleum filling events. Specifically, the north sub-section of the No. 5 fault zone experienced two petroleum filling periods during the late Caledonian and Indosinian epochs while the No. 1 fault zones and the mid-south sub-sections of the No. 5 fault zones experienced three distinct filling periods, encompassing the late Caledonian, Indosinian, and Himalayan periods. The CO2 concentrations and δ13CCO2 values suggest the presence of secondary microbial gases, primarily thermogenic gases. Gas component analysis reveals a transition from kerogen degradation gas to oil cracking gas from north to south. The detection of intact n-alkanes and compounds of the 25-norhopanes series in oil samples suggests a mixture of early biodegradable oil with late fresh oil in the area. Seismic sections reveal diabase intrusions with strong axial reflections. Local hydrothermal activities during the Permian era rapidly cracked saturated hydrocarbon biomarkers, forming polycyclic aromatic hydrocarbons in the oil. Hydrothermal activity in the south sub-section of the No. 5 fault zone depleted the hydrocarbon-generating capacity of the underlying source rocks. Petroleum charged during the Indosinian period likely originated from potential petroleum reservoirs in the Cambrian system. This explains the comparatively low temperature of the SHB57X reservoir (163.32 °C) and the lack of strong hydrothermal activity in the late stage, but no biomarkers of the second-stage charged oil have been detected. Biomarker detection and gas genesis in the mid-south sub-section of the No. 5 fault zone and in the No. 1 fault zone suggest weak or no hydrothermal activity, with Cambrian source rocks maintaining their hydrocarbon generation capacity. Gas filling in the Himalayan period caused evaporative fractionation in the original reservoirs, resulting in a disproportionate (2-MH+2,3-DMP)/(3-MH+2,4-DMP), producing high K1 values in the light hydrocarbons in the present petroleum reservoirs. Differences in gas charging events in the Himalayan period led to the present distribution of petroleum phases.

Fluid origin and evolution of the Taolin Pb-Zn deposit in northeastern Hunan Province, South China: Insights from fluid inclusions and H-O-He-Ar isotopes

Situated in northeastern Hunan Province, the vein-type Pb-Zn orebodies at Taolin are mainly hosted in NE-/NEE-trending faults between Dayunshan-Mufushan pluton and Neoproterozoic metasedimentary rocks of the Lengjiaxi Group. Hydrothermal mineralization can be divided into five stages: (1) coarse-grained quartz stage, (2) quartz-fluorite-base metal stage, (3) quartz-barite-fluorite-base metal stage, (4) pale pink and colorless quartz stage, and (5) fine-grained quartz stage. In this research, fluid inclusions as well as stable (H-O) and noble gas (He-Ar) isotope compositions were performed to uncover the nature, origin, and evolution of the ore-forming fluids, ore precipitation mechanisms, and mineralization process of the Taolin deposit. Four types of fluid inclusions, i.e., liquid-rich two-phase inclusions (LV-type), pure liquid phase inclusions (PL-type), vapor-rich two-phase inclusions (VL-type), and pure vapor phase inclusions (PV-type), were distinguished in sphalerite, quartz, and fluorite. Microthermometric analysis of fluid inclusion assemblages in sphalerite, quartz, and fluorite from different stages indicates that from the Stage 1 to Stage 5, the homogenization temperatures vary between 168 and 211 °C, between 151 and 198 °C, between 131 and 180 °C, between 132 and 164 °C, and between 118 and 138 °C, respectively, whereas the fluid salinities vary from 12.4 to 16.9 wt% NaCl equivalent, from 9.7 to 14.6 wt% NaCl equivalent, from 5.6 to 10.3 wt% NaCl equivalent, from 3.6 to 9.7 wt% NaCl equivalent, and from 0.9 to 3.8 wt% NaCl equivalent, respectively. The H-O isotope data of quartz and the He-Ar isotopic compositions of sulfide crystals suggest that the ore-forming fluids were a mixture of crust-derived magmatic hydrothermal fluid and meteoric water. Fluid mixing and cooling were likely the crucial mechanisms for ore precipitation.

The composition of apatite in the Archean Siilinjärvi glimmerite-carbonatite complex in eastern Finland

We present a geochemical dataset and cathodoluminescence images of apatite from the Neoarchean (2610 Ma) glimmerite-carbonatite rocks from the Siilinjärvi complex, Eastern Finland. The subhedral, tapered prismatic grains are compositionally fluorapatite, with limited substitution of Ca by Sr, Na and low REE and Si contents. The Sr/Y ratios are among the highest in a global apatite comparison, comparable to those from other calcite carbonatites, dolomite carbonatites, and phoscorites. Some grains show evidence of late- or post-magmatic interaction with a carbonatite magma or a hydrothermal fluid, resulting in REE-rich overgrowth rims or recrystallized grains with abundant fluid inclusions. We interpret the high Sr/Y ratios combined with low REE contents and depleted heavy REE+Y to represent crystallization from a mantle-derived carbonatite parental magma. We show that the Siilinjärvi apatite is chemically heterogeneous but with a limited range in compositions. There are noticeable compositional differences on all spatial scales from micrometer to tens of meters, i.e., within a single crystal, between crystals in a sample, between samples and the two individual sampling locations. We conclude that the intra-crystal geochemical variability in apatite is a suitable tracer of the magmatic and post-magmatic evolution of carbonatite complexes.

Multiphase evolution of fluids in the Rudnik hydrothermal-skarn deposit (Serbia): new constraints from study of quartz-hosted fluid inclusions

Multiphase evolution of fluids in the Rudnik hydrothermal-skarn deposit (Serbia): new constraints from study of quartz-hosted fluid inclusions

Clorine Solubility in Silicate Melts: New Experiments and Thermodynamic Mixing Model

We present new experimental data on Cl solubility in model basalt melts of eutectic compositions diopside (Di)–albite (Ab) and Di–anorthite ± quartz (Qtz). The starting glasses were equilibrated with aqueous fluid H₂O-NaCl-CaCl₂ at 4 kbar in the temperature range 900–1200°C. The experiments show that the Cl solubility decreases with increasing NaCl in the fluid. Ca-Na partitioning between melts and fluid is weekly temperature dependent and resembles that of the plagioclase-fluid system. The new experimental data, along with the previously published results on the model granite melting in the presence of (Na, K)Cl brines (Aranovich et al., 2013) are used to calibrate an empirical thermodynamic model for the salt species (NaCl, KCl, CaCl₂) in silicate melt. Calculations show that Cl solubility in the haplogranite melt decreases with increasing K/Na ratio in the fluid (and, correspondingly, melt). At high pressure (10 kbar) Cl solubility in the granite increases with increasing H₂O content. Calculated phase diagram for a simple pseudo-ternary system Ab–H₂O–NaCl demonstrates complex phase relations and, correspondingly, evolution of the H₂O and NaCl concentrations in the melt. Literature data on the variations of H₂O and NaCl in the melt and fluid inclusions in Qtz from the granite of Badzhal tin deposit is used to illustrate complex evolution of a fluid-magmatic system.

Understanding the burial history and the hydrocarbon potential of the late Paleozoic Claromecó foreland Basin (Southwestern Gondwana, Argentina) by combining organic geochemistry, organic petrology, and thermal modeling

The Claromecó foreland Basin (Carboniferous–Permian; southern Buenos Aires province, Argentina) is key to understanding the paleotectonic evolution of the southwestern Gondwana margin and is relevant to energy resource exploration. This study reconstructs the thermal and burial history of the Claromecó Basin by integrating geochemical data, organic petrology, and thermal modeling techniques. Cores samples of the Tunas Formation (Pillahuincó Group, Early Permian) were studied. A 1D thermal model was constructed, calibrated with vitrinite reflectance measurements (VRo %), and corroborated with fluid inclusion and apatite fission track data from previous studies. Rock-Eval pyrolysis results show TOC% values ranging from 0.13 to 60.35 wt%. The Hydrogen index (HI < 50 mg HC/g TOC) and Oxygen index (OI < 50 mg CO2/g TOC) indicate the dominance of Type III and Type IV kerogens, most likely resulting from the thermal maturation of an original Type III kerogen. Petrologic observations confirm the presence of macerals from the inertinite group, as well as minor amounts of vitrinite and liptinite. The Tmax displays a temperature range mostly from 460 to 610 °C. The VRo % values range from 1.5 to 2.0%. Geochemical data combined with VRo % measurements confirm a late catagenesis to metagenesis stage within the wet to dry gas window for coals and organic-rich strata.In order to constrain the thermal evolution of the basin infill, different scenarios were tested by varying the heat flow and the missing section thickness associated with the uplift and erosion of the basin (Permian–Cenozoic unconformity). The best calibration results were obtained with an erosion thickness of 3000 up to 4200 m and paleo heat flow peaks of either 60 or 80 mW/m2 during the Lower Permian–Lower Cretaceous. The Tunas Formation was deposited and buried during the Permian–Triassic (Gondwanides Orogeny phase), reaching a maximum temperature of 180 °C. The results obtained by combining geochemical analysis, organic petrology, and thermal modeling techniques indicate that the coal beds of the Tunas Formation could have a current potential as gas-prone source rocks. Despite that, the hydrocarbon generation capacity of coal levels is currently low due to the high percentage of residual (Type IV) kerogen. Further research could help clarify if the hydrocarbons potentially expelled by these source rocks have been lost due to migration or could be trapped somewhere in the basin.

Diagenesis and mineralization in the Central African Copperbelt, implications from the reflectance of pyrobitumen and Kübler (illite crystallinity) index

The Central African Copperbelt stands out as one of the world's largest sediment-hosted Cu-Co provinces, contributing to over 60% of global Co production. A comprehensive basin analysis approach is imperative for unraveling the ore-forming processes, encompassing an understanding of the diagenesis or metamorphism that the mineralized rocks underwent. In this study, two types of pyrobitumen (burial related and burial plus hydrothermal related) reflectance values have been measured, which record maximum temperatures during deep burial and hydrothermal imprint. The calculated temperatures provide important information about the maximum burial and hydrothermal fluid temperatures in distinct regions of the Copperbelt. The average burial related pyrobitumen reflectance for Nkana, the southeastern part of the Copperbelt, ranges between 3.43 and 3.75% BRr, indicating a maximum burial temperature of about 240 °C. Moving towards the central part of the Copperbelt at Luiswishi, the average pyrobitumen reflectance varies between 2.65 and 2.87% BRr, with calculated maximum burial temperatures reaching about 220 °C. In the northwestern part (Tenke Fungurume mining district, TFMD), the maximum burial temperatures decrease to approximately 200 °C, based on the calculation of pyrobitumen reflectance at 2.10% BRr. This decreasing temperature trend from southeast to northwest corresponds to the observed decrease in metamorphic grade across the Copperbelt, ranging from amphibolite and upper greenschist facies in the Zambian part to prehnite-pumpellyite facies in the Congolese Copperbelt. The temperatures calculated during maximum burial, especially at the Nkana ore deposit, are lower than those previously proposed based on the mineralogy of the rocks, i.e. upper greenschist facies. However, the latter does correspond to the temperatures reached by the mineralizing fluids in this area and thus rather reflects the alteration assemblage and temperature. The average burial plus hydrothermal related pyrobitumen reflectance measured at TFMD ranges between 3.06 and 5.36% BRr, indicating calculated average temperatures of 300–350 °C. These temperatures align with those recorded for the late diagenetic to syn-orogenic mineralization by fluid inclusion microthermometry (180–340 °C) at TFMD. The data suggests a pervasive migration of hydrothermal fluid through the rocks, contributing to the observed pyrobitumen reflectance. The illite crystallinity of the examined samples is notably high. At Nkana, the KI values range between 0.10 Δ°2θ and 0.22 Δ°2θ, for Luiswishi between 0.12 Δ°2θ and 0.24 Δ°2θ, for Kamoto between 0.17 Δ°2θ and 0.23 Δ°2θ, for TFMD between 0.17 Δ°2θ and 0.25 Δ°2θ, which indicates all these samples were placed in epizone, with only a few in anchizone. This high value could be attributed to two potential factors: the admixing of detrital muscovite to the sediments or the influx of potassium due to the pervasive alteration throughout the Copperbelt, but the latter one is less likely since the selected samples show no evidence of alteration.

Fluid and solid inclusions in large halite veins in the Kłodawa Salt Dome (Central Poland) – insights into its development

Secondary rocks are often found in salt domes. Among these, large halite crystal (LHC) veins and nests are common, as in the Kłodawa Salt Dome of Poland. Mineralogical tests carried out on LHC here showed the presence of fluid and solid inclusions in the halite crystals. The halite itself commonly exhibits birefringence, suggesting lattice stresses. Among the solid inclusions, anhydrite is the most common. Three types of anhydrite crystals have been distinguished as regards their size and occurrence, while small, rounded inclusions of sylvite appear much less frequently. Fluid inclusions are generally rare and mostly of the secondary type. This type of fluid inclusion assemblage (FIA) comprises various kinds as regards their size and shape, as well as in their liquid-to-gas phase ratio. Primary FIAs are of two types: small, chevron-like inclusions containing sylvite daughter minerals, and large liquid-gas inclusions with carnallite and other daughter minerals. The melting temperature of sylvite ranged from 90 to 278°C, and for carnallite from 68 to 142°C. Complete homogenization of the inclusions took place at temperatures between 260 and 471.2°C. This indicates the high-temperature origin of the LHC and the presence of significant amounts of K+, Mg+2, Ca+2, and SO4-2 ions in the solutions.

The Spatial and Temporal Evolution of the Sadisdorf Li-Sn-(W-Cu) Magmatic-Hydrothermal Greisen and Vein System, Eastern Erzgebirge, Germany

Abstract The Sadisdorf Li-Sn-(W-Cu) prospect in eastern Germany is characterized by vein- and greisen-style mineralization hosted in and around a small granite stock that intruded into a shallow crustal environment. The nature and origin of this mineral system are evaluated in this contribution by a combination of petrography and fluid inclusion studies, complemented by Raman spectroscopy and whole-rock geochemical analyses. The early magmatic-hydrothermal evolution is characterized by a single-phase low-salinity (7.0 ± 4 wt % NaCl equiv), high-temperature (&amp;gt;340°C), CO2-CH4–bearing aqueous fluid, which caused greisen alteration and mineralization within the apical portions of the microgranite porphyry. The bimodal distribution of brine and vapor fluid inclusions, and the formation of a magmatic-hydrothermal breccia associated with the proximal vein mineralization are interpreted to mark the transition from lithostatic to hydrostatic pressure. The vein- and stockwork-style mineralization (main stage) displays lateral zonation, with quartz-cassiterite-wolframite-molybdenite mineral assemblages grading outward into base-metal sulfide-dominated assemblages with increasing distance from the intrusion. Late fluorite-bearing veinlets represent the waning stage in the evolution of the mineral system. The similarity in the homogenization temperature (250°–418°C) of fluid inclusions in quartz, cassiterite, and sphalerite across the Sadisdorf deposit suggests that cooling was not a significant factor in the mineral zonation. Instead, fluid-rock interaction along the fluid path is considered to have controlled this zonation. In contrast to quartz-, cassiterite- and sphalerite-hosted fluid inclusions, which have a salinity of 0.0 to 10.0 wt % NaCl equiv, the fluid inclusions in late fluorite veins that overprint all previous assemblages have a salinity of 0.0 to 3.0 wt % NaCl equiv and homogenize at temperatures of 120° to 270°C, thus indicating cooling with or without admixture of meteoric fluids during the waning stage of the mineral system. The Sadisdorf deposit shares similar characteristics with other deposits in the Erzgebirge region, including a shallow level of emplacement, similar mineralization/alteration styles, and a hydrothermal evolution that includes early-boiling, fluid-rock interaction, and late cooling. In contrast to most systems in the region, both proximal and distal mineralization are well preserved at Sadisdorf. The recognition of such spatial zoning may be a useful criterion for targeting greisen-related Li and Sn resources.

Direct evidence of gas flushing oil in deep reservoirs: Insight from integrated fluid inclusion analyses

Gas flushing of oil has been proposed as an essential process for forming some condensate gas reservoirs based on laboratory experiments and modeling but such a process has rarely been documented in subsurface reservoirs. Here, we report a unique type of yellow-ringed oil inclusions (YROIs) discovered from a deep reservoir in the Kuqa Foreland Basin, Western China that recorded the gas flushing of oil process in the subsurface. The occurrence, composition, phase state and PVT conditions of YROIs during trapping were investigated using a suite of fluid inclusion analytical methods including fluid inclusion petrography, microthermometry, fluorescence spectroscopy, PVT modeling and molecular composition analysis.YROIs found in the reservoir are three-phase (solid–liquid-vapor) fluid inclusions at room temperature with solid rings of 2–3 μm thickness and estimated volume percentages varying between 5 % and 15 %. When heated the solid ring starts to melt at around 46 °C and homogenized with the liquid phase at or above their corresponding homogenization temperatures of coeval aqueous inclusions. YROIs have fluorescence spectral peaks between 530 nm and 550 nm and an elevated spectral shoulder around 650 nm when measured at room temperature; but most spectra show a distinct “blue shift” and an absence of the 650 nm shoulder when measured at their homogenization temperatures. Some YROIs with thick yellow rings show dual spectral peaks at 570 nm and 630 nm at room temperature and their spectral peaks do not change when remeasured at their homogenization temperatures. Molecular compositions derived from synchronous fluorescence spectra and GC-MS analysis suggest that the compositions of YROIs are rich in polyaromatic compounds. PVT modeling indicates that YROIs were trapped under high pressure conditions with a pressure exceeding 50 % of the corresponding hydrostatic pressure.YROIs are interpreted to have been trapped under an elevated temperature and overpressure condition (around 110 °C and 60 MPa) relating to an intensive (wet) gas flushing of an early-charged wax-rich oil. When light hydrocarbon components in the reservoir oil were partially removed by gas, the wax/resin components rich in polyaromatic hydrocarbon compounds may precipitate due to physio-chemical fractionation. YROIs were entrapped in subsurface from a heterogeneous hydrocarbon fluid containing variable amounts of wax/resin colloids, which subsequently coalesce to form solid rings adhering to the inner wall of oil inclusions at room temperature. The presence of yellow-ringed oil inclusions in a reservoir may be indicative of a rapid gas flushing of waxy oil under high pressure, and their minimum homogenization temperature may approximate their trapping temperature.

Microtextural evidence for the recrystallization of opal-A to quartz in epithermal veins: A case study from the McLaughlin deposit, California

High-grade ores in low-sulfidation epithermal deposits commonly consist of banded veins containing quartz as the most abundant gangue mineral. Previous studies suggested that at least some of the quartz has formed as a product of recrystallization from a noncrystalline silica precursor. Detailed petrographic studies confirm that high-grade veins from the <2.2 Ma McLaughlin deposit in California were originally entirely composed of opal-AG. The noncrystalline silica is isotropic in crossed-polarized light and consists of compacted microspheres that are up to several micrometers in size. In many bands of the high-grade veins, the thermodynamically unstable opal-AG has matured to quartz. The recrystallization of the noncrystalline silica resulted in the development of quartz and ore textures that mask the original conditions of vein formation. Incipient recrystallization of the opal-AG caused the formation of lepispheres consisting of opal-CT as well as the development of concentrically banded silica spheres. Continued maturation led to the growth of elongated quartz crystals or complexly shaped quartz aggregates in the cores of the concentrically banded silica spheres. Amalgamation of quartz crystals caused the development of mosaic quartz or flamboyant quartz. Ripening produced large prismatic quartz crystals, which are characterized by zones of feathery appearance. Fluid inclusions within the quartz formed through recrystallization are typically highly irregular in shape and show inconsistent liquid-to-vapor volumetric proportions, but assemblages with consistent ratios are also present. Bands rich in fluid inclusions occurring along former recrystallization fronts in prismatic quartz crystals resemble growth zones in zonal quartz. Recrystallization of the silica matrix resulted in grain coarsening of the ore minerals and encapsulation of ore minerals by quartz. In areas where recrystallization of the noncrystalline silica proceeded to completeness, the quartz textures could be easily misinterpreted to indicate that quartz growth occurred in open space with the ore minerals infilling vug spaces. Correct recognition of recrystallization textures has significant implications for paragenetic investigations on vein material from epithermal deposits as well as the design of fluid inclusion studies.

Genesis of Hongqiling Sn-W polymetallic deposit in Dongpo ore concentration field, southern Hunan: Evidences from U-Pb chronology and trace element geochemistry of cassiterite

Hongqiling deposit is one of the most typical hydrothermal vein type Sn-W polymetallic deposits in the Dongpo ore field, southern Hunan. It is an ideal object to study the Sn-W mineralization in the Nanling metallogenic belt and even in the whole South China Block, and to reveal the regional metallogenetic regularity. Based on the detailed investigation of the deposit geology, this paper discusses the mineralization age and processes of the Hongqiling hydrothermal vein type Sn-W polymetallic deposit by LA-MC-ICP-MS in-situ U-Pb dating and trace element geochemistry of cassiterite from the quartz vein type Sn-W ore body. Cathodoluminescence (CL) imaging shows that cassiterite in Hongqiling deposit can be divided into two generations.primary cassiterite (Cst-I) and altered cassiterite (Cst-II). The LA-MC-ICP-MS in-situ U-Pb age of the two groups of Cst-I samples are 158.9 ± 0.7 Ma and 158.4 ± 0.8 Ma, respectively, which are well consistent with the mineralization ages of most Sn-W deposits in the Nanling metallogenic belt, and are also consistent with the ages of middle to late Jurassic magmatic activity represented by the Qianlishan intrusion. This indicates that the Hongqiling deposit, like many Sn-W deposits in the Nanling metallogenic belt, is genetically related to the regional Middle to Late Jurassic granitic magmatic activities. LA-ICP-MS trace element analysis shows that trace elements such as Na and Cs are mainly distributed in fluid inclusions in cassiterite, while the major elements such as Mg, Al, and Si are mainly distributed in the mineral inclusions, and other elements such as W, U, Zr, Hf and Ti are mainly distributed in the cassiterite by isomorphic substitution. The high Fe and W contents in both primary and altered cassiterite indicate that the ore-forming fluid of Hongqiling deposit is mainly derived from granitic magma. The fluctuating variation of Fe, V, Sc, Ti, Zr, Hf, Nb and Ta in the primary cassiterite with the crystalline bands indicates that there are two large-scale pulses of magmatic hydrothermal fluid during the mineralization process, while the altered cassiterite is relatively depleted of Ti, Sc, Zr and U elements, and enriched in Pb which may represent the compositional characteristics of the late-stage fluid. In summary, the Hongqiling hydrothermal vein type Sn-W polymetallic deposit was formed by the pulsating exsolution of magmatic hydrothermal fluid of late Jurassic granitic magmatism. The trace elemental compositions of primary cassiterite are generally controlled by the compositions of ore-forming fluid and the rate of crystallization.

Magmatic Storage and Volatile Fluxes of the 2021 La Palma Eruption

AbstractThe 2021 La Palma eruption (Tajogaite) was unprecedented in magnitude, duration, and degree of monitoring compared to historical volcanism on La Palma. Here, we provide data on melt inclusions in samples from the beginning and end of the eruption to compare the utility of both melt and fluid inclusions as recorders of magma storage. We also investigated compositional heterogeneities within the magmatic plumbing system. We found two populations of olivine crystals: a low Mg# (78–82) population present at the beginning and end of eruption, recording the maximum volatile contents (2.5 wt % H2O, 1,800 ppm F, 700 ppm Cl, 3,800 ppm S) and a higher Mg# (83–86) population sampled toward the end of the eruption, with lower volatile contents. Despite their host composition, melt inclusions share the same maximum range of CO2 concentrations (1.2–1.4 wt %), indicating olivine growth and inclusion capture at similar depths. Overall, both melt and fluid inclusions record similar pressures (450–850 MPa, ∼15–30 km), and when hosted in the same olivine crystal pressures are indistinguishable within error. At these mantle pressures, CO2 is expected to be an exsolved phase explaining the similar range of CO2 between the two samples, but other volatile species (F, Cl, S) behave incompatibly, and thus, the increase between the two olivine populations can be explained by fractional crystallization prior to eruption. Finally, based on our new data, we provide estimates on the total volatile emission of the eruption.

Deciphering ore genesis with oxygen and sulfur isotope signatures: A case study from the Singhbhum Shear Zone, Eastern India

The importance of light-stable isotopes and their mass-dependent fractionations in understanding past geological processes is enormous. The present research delivers precise, high-resolution, in-situ oxygen (18/16O) and triple sulfur (32/33/34S) isotope ratios from quartz and sulfide minerals found in the CuAu Kendadih deposit located along the Mesoproterozoic (∼1.6 Ga) Singhbhum Shear Zone (SSZ) in eastern India. Oxygen and sulfur isotope analyses were carried out on quartz and pyrite-chalcopyrite pairs that are in textural equilibrium, using the most advanced Large Geometry-Secondary Ion Mass Spectrometer (LG-SIMS; CAMECA IMS-1300HR3). The results show restricted ranges for δ18Oquartz (+6 to +7.7‰; average: 6.9 ± 0.9‰, n = 50) and δ34Schalcopyrite-pyrite (+11.4 to +11.9‰; average: 11.79 ± 0.2‰, n = 62). This isotopic homogeneity suggests a single, uniform fluid source for the ore-forming metals. The combined oxygen, sulfur isotope ratios, and fluid inclusion data are consistent with a hydrothermal fluid derived from an “I-type” granitic melt. This study incorporates existing fluid inclusion, stable, and radiogenic isotope data from temporally similar deposits within the shear zone, reevaluating their implications in light of the new findings. It proposes that, around 1.6 billion years ago, underplating the Singhbhum Craton by the Dalma Plume resulted in the remelting of the lower crust. This remelting is attributed to the plume's introduction of a significantly elevated thermal perturbation. The process is hypothesized to have led to the generation of second-order granitic melts. Upon emplacement in the lower crust, these granitic melts became the potential source for essential metals, ligands, and hydrothermal fluids, contributing to mineralization within the deep-seated Singhbhum Shear Zone. This research attempts to comprehensively describe the “source-to-sink” ore genesis model by proposing potential magma chamber processes that concentrate metals and ligands at the roof zone, followed by the separation of metal-rich hydrothermal fluids, fluid-rock interaction, and the physicochemical conditions governing the deposition of the extensive polymetallic deposit. This work offers novel insights into the Mesoproterozoic metallogenesis along the Singhbhum Shear Zone, challenging existing paradigms that favored evaporite or seawater brine sources. Furthermore, it sheds light on the Mesoproterozoic sub-crustal processes beneath the Indian Craton in this region.

The Chain of Processes Forming Porphyry Copper Deposits—An Invited Paper

Abstract Porphyry-related mineral deposits are giant geochemical anomalies in the Earth’s crust with orders-of-magnitude differences in the content and proportion of the three main ore metals Cu, Au, and Mo. Deposit formation a few kilometers below surface is the product of a chain of geologic processes operating at different scales in space and time. This paper explores each process in this chain with regard to optimizing the chances of forming these rare anomalies. On the lithosphere scale, deposits with distinct metal ratios occur in provinces that formed during brief times of change in plate motions. Similar metal ratios of several deposits in such provinces compared with global rock reservoirs suggest preceding enrichment of Au or Mo in lithospheric regions giving rise to distinct ore provinces. The largest Cu-dominated deposits and provinces are traditionally explained by selective removal of Au during generation or subsequent evolution of mantle magmas, but the possibility of selective Cu pre-enrichment of lithosphere regions by long-term subduction cannot be dismissed, even though its mechanism remains speculative. Evolution of hydrous basaltic melts to fertile magmas forming porphyry Cu deposits requires fractionation toward more H2O-rich magmas in the lower crust, as shown by their adakite-like trace element composition. The prevailing interpretation that this fractionation leads to significant loss of chalcophile ore metals by saturation and removal of magmatic sulfide might be inverted to a metal enrichment step, if the saturating sulfides are physically entrained with the melt fraction of rapidly ascending magmas. Ascent of fertile magma delivers a large mass of H2O-rich ore fluid to the upper crust, along points of weakness in an overall compressive stress regime, within a limited duration as required by mass and heat balance constraints. Two mechanisms of rapid magma ascent are in debate: (1) wholesale emplacement of highly fractionated and volatile-rich granitic melt into a massive transcrustal channelway, from which fluids are exsolved by decompression starting in the lower crust, or (2) partly fractionated magmas filling a large upper crustal magma chamber, from which fluids are expelled by cooling and crystallization. Transfer of ore-forming components to a hydrothermal ore fluid is optimized if the first saturating fluid is dense and Cl rich. This can be achieved by fluid saturation at high pressure, or after a moderately H2O rich intermediate-composition melt further crystallizes in an upper crustal reservoir before reaching fluid saturation. In either case, metals and S (needed for later hydrothermal sulfide precipitation) are transferred to the fluid together, no matter whether ore components are extracted from the silicate melt or liberated to the ore fluid by decomposition of magmatic sulfides. Production and physical focusing of fluids in a crystallizing upper crustal magma chamber are controlled by the rate of heat loss to surrounding rocks. Fluid focusing, requiring large-scale lateral flow, spontaneously occurs in mushy magma because high water content and intermediate melt/crystal ratio support a network of interconnected tubes at the scale of mineral grains. Calculated cooling times of such fluid-producing magma reservoirs agree with the duration of hydrothermal ore formation measured by high-precision zircon geochronology, and both relate to the size of ore deposits. Ore mineral precipitation requires controlled flow of S- and metal-rich fluids through a vein network, as shown by fluid inclusion studies. The degree of hydrothermal metal enrichment is optimized by the balance between fluid advection and the efficiency of cooling of the magmatic fluid plume by heat loss to convecting meteoric water. The depth of fluid production below surface controls the pressure-temperature (P-T) evolution along the upflow path of magmatic fluids. Different evolution paths controlling density, salinity, and phase state of fluids contribute to selective metal precipitation: porphyry Au deposits can form at shallow subvolcanic levels from extremely saline brine or salt melt; high-grade Au-Cu coprecipitation from coexisting and possibly rehomogenizing brine and vapor is most efficient at a depth of a few kilometers; whereas fluids cooling at greater depth tend to precipitate Cu ± Mo but transport Au selectively to shallower epithermal levels. Exhumation and secondary oxidation and enrichment by groundwater finally determine the economics of a deposit, as well as the global potential of undiscovered metal resources available for future mining.