Meteoric Fluids Research Articles

Lead isotope geochemistry of plagioclase in the Skaergaard intrusion by LA-ICP-MS: Assessing the effects of crustal contamination and link with East Greenland flood basalts

The Skaergaard intrusion of East Greenland is one of the best studied layered intrusions on Earth and preserves an exceptional rock record produced during low-pressure, closed-system crystallization of Fe-rich tholeiitic magma. The lead isotope compositions of plagioclase feldspar in cumulates and related igneous rocks of the Skaergaard intrusion were determined directly from single spot analyses in thin section by laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) (n = 757). Plagioclase primocrysts, typically with <2 ppm Pb, and feldspar in interstitial pockets from the Layered Series and from most of the Marginal Border Series have the same Pb isotope compositions within analytical uncertainty (208Pb/206Pb = 2.20 ± 0.06; 207Pb/206Pb = 0.889 ± 0.028). There are no significant Pb isotope differences between cores and rims of individual plagioclase primocrysts or between different types of interstitial pockets (e.g., interstitial granophyre, symplectites). These Pb isotope compositions are less radiogenic than those from most of the contemporaneous East Greenland flood basalts indicative of crustal contamination at deeper crustal levels prior to emplacement. Plagioclase from three samples of the Marginal Border Series adjacent to host gneisses (<5 m from the contact) have higher 208Pb/206Pb (2.30 ± 0.06, 2.35 ± 0.02, 2.51 ± 0.21) compared to the rest of the intrusion. These results confirm that crystallization of the Skaergaard intrusion occurred under essentially closed-system conditions with localized minor incorporation of “amphibolitic” gneiss. Hydrothermal alteration occurred at near-solidus to subsolidus conditions by circulating meteoric fluid that had equilibrated with the overlying flood basalts. This alteration resulted in albitized interstitial granophyre and rare spot analyses from plagioclase primocrysts characterized by Pb isotope compositions comparable to those of the flood basalts. Granophyres of different origins (e.g., transgressive granophyre, granophyric segregation) have variable Pb isotope compositions (208Pb/206Pb = 2.09–2.51; 207Pb/206Pb = 0.844–1.013) that are distinct from the Skaergaard cumulates. Based on Pb isotope systematics, combined with published SrNd isotopic compositions and 40Ar/39Ar geochronology from East Greenland and Faroe Island basalts, the Skaergaard intrusion is linked to eruption of the earliest of the Plateau Basalts in East Greenland (Milne Land Formation) during continental breakup and opening of the North Atlantic Ocean. This microanalytical study highlights the ability to conduct rapid Pb isotopic measurements in low-Pb concentration materials (e.g., <2 ppm Pb in plagioclase) at high spatial resolution by LA-ICP-MS with precision sufficient to constrain a range of magmatic processes in layered intrusions and other feldspar-bearing rocks preserved in the geological record.

Diagenetic controls on porosity evolution and reservoir quality of an outcrop analogue of the Jurassic carbonate reservoirs in the Arabian Plate: An example from the Middle Jurassic Tuwaiq Mountain Formation, Central Saudi Arabia

The Middle Jurassic Tuwaiq Mountain Formation (TMF; formed of three members, from bottom to top T1, T2, and T3) represents one of the primary conventional and unconventional reservoirs to be assessed in Saudi Arabia. It is considered as a tight carbonate reservoir in the Jafurah Basin and conventional reservoir in the Arabian Basin. Here, we investigate the depositional, diagenetic, and stratigraphic impact on reservoir quality and porosity evolution of the TMF through an integrated petrographical, geochemical and petrophysical analyses on outcrop samples. The TMF has a complex diagenetic history including micritization, dissolution, recrystallization and neomorphism, meteoric cementation, evaporite precipitation, dolomitization, silicification, dolomite dissolution and calcitization. Dolomitization occurred via a hypersaline fluid mechanism, based on texture, association with evaporites, and Sr concentration. X-ray diffraction results support chert replacing evaporite as the mechanism of the two chert beds in the T3 member due to the presence of anhydrite relics in their samples. This replacement formed the necessary Ca 2+ rich fluid for dolomite dissolution and calcitization. Therefore, dolomite calcitization occurs locally and is stratigraphically controlled based on its position relative to chert beds in T3. T3 and the upper part of the T2 member contain calcitized dolomites, while the lower part of T2 and T1 contain only dissolved dolomite. As the fluid went deeper in the TMF, it became weaker. Therefore, the fluid was too weak to develop dolomite calcitization process and instead only affected T1 and the lower part of T2 by dolomite dissolution. Overall, dolomite dissolution and dolomite calcitization didn't have a high impact on porosity evolution as the TMF isn't a highly dolomitized formation. The distribution of porosity (ø), permeability (K), and reservoir-quality-index (RQI) of the TMF are stratigraphically controlled. The TMF represents the regressive system tract of a 3rd order depositional sequence, which is composed of seven 4th order cycles (i.e. deep lagoon cycles (DLC) and shallow lagoon cycles (SLC)). RQI, Ø, and K plots showed great fitting with the 4th order depositional-cycles as DLC has very poor reservoir properties (average ø = 7.7%, average K = 0.17 mD, average RQI = 0.03), while SLC has fair reservoir properties (average ø = 15.4%, average K = 2.64 mD, average RQI = 0.11). Reservoir quality contrast is controlled by two factors: (1) the reduced mud-content and increased grain-content in SLC compared with DLC resulted in increased primary interparticle porosity, and is governed by depositional energy; and (2) the higher primary interparticle porosity in SLCs compared with DLCs preferentially facilitated more infiltration of undersaturated meteoric fluids, resulting in enhanced grain dissolution. This is reflected on the higher proportion of moldic and vuggy porosity in SLCs compared with DLCs. The accurate assessment of the TMF micro-scale attributes and controls on reservoir quality in an outcrop analogue that occurs in close proximity to subsurface hydrocarbon producing intervals can provide important input for oilfield appraisal and enhanced oil recovery performance. • Cementation was the main destructive diagenetic feature of the reservoir quality. • Depositional texture controlled primary porosity and dissolution related secondary porosity. • Dolomite-Calcitization and meteoric-dissolution had a stratigraphically controlled distribution. • Dolomitization happened through hypersaline fluids like many Jurassic carbonates in the Arabian Plate. • Dedolomitization mechanism was related to the process of chert replacing evaporites.

Host rock petrology, hydrothermal alteration characteristics & ore mineralogy of porphyry copper-gold deposit, Brambang, Lombok, West Nusa Tenggara Indonesia

Several world-class porphyry copper–gold deposits/prospects have been discovered in the eastern Sunda arc. One copper–gold prospect area is located at Brambang, Sekotong District, West Lombok Regency, West Nusa Tenggara Province, Indonesia This study is aimed to understand a preliminary geological framework, which characterizes the Brambang deposit in terms of the host rock, hydrothermal alteration characteristics, and ore mineralogy studies of the deposit. Fieldworks and several laboratory analyses were performed including petrography, ore mineralogy and X-ray diffraction (XRD). Host rock was dominated by volcanic rocks consisting of dacitic volcanic rock, diatreme breccia, and diorite intrusion. The hydrothermal alteration is characterized by argillic alteration (kaolinite-illite-smectite), propylitic (chlorite-epidote-calcite), and potassic (quartz-biotite-actinolite-magnetite), with the presence of sulfide minerals such as pyrite (FeS2), chalcopyrite (CuFeS2), and chalcocite (Cu2S), and the oxide minerals such as magnetite (Fe3O4), and hematite (Fe2O3). The alteration zone stage in the study area begins with forming a quartz-biotite-magnetite (potassic zone) formed at a high temperature of around 300–360 °C and at pH 7–8. This stage is followed by forming a chlorite-epidote-calcite (propylitic zone) outside the potassic zone, at a temperature range of 290–340 °C and pH of 5–6, which indicates a hydrothermal system cooling process. Then, due to the increasing influx of meteoric fluid that enters the fractures formed due to fault activity, a quartz-kaolinite-illite (argillic zone) is formed with a temperature range of 130–210 °C and pH 4–6. The presence of diatreme breccia and stockwork within the mineralization in the Brambang deposit supported the theory related to porphyry copper–gold deposits.

Tracing fluid evolution in sedimentary basins with calcite geochemical, isotopic and U-Pb geochronological data: Implications for petroleum and mineral resource accumulation in the Nanpanjiang Basin, South China

AbstractFluid migration in sedimentary basins enable mass and energy transport and play critical roles in geochemical and geodynamical evolution of sedimentary basins. Moreover, reconstructing sedimentary basin fluid evolution from the geological record aids in constraining the evolution of associated petroleum and mineralization systems. As a relict of fluid flow activity, calcite is often a record of fluid flow and therefore can be used to characterize the fluids responsible for its precipitation.Here we study the Nanpanjiang Basin in South China where petroleum reservoirs and Carlin-type gold deposits spatially coincide. Through in situ U-Pb dating and geochemical analysis (87Sr/86Sr, δ18OVienna standard mean ocean water, δ13CVienna Peedee belemnite, rare earth elements) of calcite, this work constrains the key times related to petroleum migration/accumulation and Carlin-type gold mineralization, defines the basin fluid evolution, and proposes a genetic model for petroleum accumulation and gold mineralization within the Nanpanjiang Basin. The U-Pb age (ca. 241.4 Ma) for the gray/black calcite related to bitumen indicates the petroleum migration/accumulation occurred during the Triassic. The U-Pb date (ca. 106–121 Ma) of the white calcite associated with the gold-bearing pyrite, realgar, and fluorite record the lower timing limit of the Carlin-type gold systems. The geochemical data suggest both calcite types are cogenetic but suffered complex evolution with the gray/black calcite precipitating under low temperatures related to the continuous basin burial and the white calcite affected by post formation alteration related to both hydrothermal and meteoric fluids. Combined with the regional tectonic history, the Early Triassic petroleum migration/accumulation and the Early Cretaceous secondary Carlin-type gold mineralization events are considered to be related to the collision between the Indo-China and South China blocks, and the subduction between the Paleo-Pacific and Eurasian plates, respectively.

Triple oxygen isotope systematics of diagenetic recrystallization of diatom opal-A to opal-CT to microquartz in deep sea sediments

The oxygen-18 isotopic composition (δ18O) of silica preserved in oceanic sediments is an important archive of Earth’s temperature and/or seawater δ18O from the Archean to present. Recent advances in high-precision measurements of both δ18O and δ17O values have been used to provide additional constraints on what the oxygen isotopic composition of chert reflects about past conditions. Here, we examine the effects on the triple oxygen isotopic composition of chert that occurs during transformation and recrystallization of biogenic opal-A to opal-CT to microquartz in deep sea sediments. We studied late Miocene to present samples from the Sea of Japan at ODP Site 795 and measured biogenic diatom opal-A, opal-CT, microquartz chert, and ‘altered’ opal-A samples—previously measured for δ18O values only—for both δ18O and δ17O values. We find that δ18O decreases and Δ′17O increases (where Δ′17O = δ17O – 0.528 × δ18O) with depth, coincident with the conversions from diatom opal-A to opal-CT to microquartz. Silica samples deviate from the trend expected for triple oxygen isotopic equilibrium with modern seawater. To explain these data, we developed a model that shows that local temperature gradients and pore fluid δ18O profiles in combination lower the measured opal-CT and microquartz δ18O values and raise the Δ′17O values relative to the initial opal-A, but deviate from triple oxygen isotopic equilibrium with seawater. We find that a steeper local temperature gradient and a larger influence of hydrothermal alteration of basalt at the base of the sediment column (which lowers pore fluid δ18O values) in the past explain both the measured δ18O and Δ′17O values of the opal-CT and microquartz.These data and our modeling show that the transformation of opal-A to microquartz in marine sediments at elevated temperatures and in the presence of lowered pore water δ18O values leads to an array that falls below the theoretical triple oxygen isotope line of equilibrium for SiO2 with modern seawater. Further, our model indicates that opal-CT and microquartz do form in triple oxygen isotopic equilibrium with pore fluids that are offset in their triple oxygen isotopic composition compared to seawater due to fluid-rock alteration of igneous rocks at the base of the sediment column. The diagenetic processes taking place in the Japan Sea do not explain a large portion of the existing Archean to present triple oxygen isotope chert data, which likely require either changes in the oxygen isotopic composition of the source water (i.e., ocean water) and/or alteration by meteoric fluids. Further, our data demonstrate that the triple oxygen isotopic composition of preserved chert need not represent surface conditions, but instead may reflect processes that occur in subsurface sediments at elevated temperatures and with modified pore fluid oxygen isotopic compositions.

Geochemical and microtextural properties of veins in a potential high-level radioactive waste disposal site

In this study, geochemical and petrographic characteristics of veins from the Permian Boda Claystone Formation (Mecsek Mts., Hungary) are presented. Understanding the connection between these properties is vital in the reconstruction of paleofluid history and tectonic evolution of this potential high-level radioactive waste disposal site. Each of the observed four vein generations consists of several mineral phases and has complex evolution, which can be attributed to multiple diagenetic and tectonic processes. Syntaxial and antitaxial veins have been observed suggesting oscillatory advective and diffusive material transport mechanisms; however, veins associated with mobile hydrofractures have also been detected. The parent fluids with a predominant temperature of 100–150 °C and variable salinity (3.5–13.7% wNaCleq) originated potentially by mixing of connate brine with freshwater released by smectite-to-illite transition and isotope exchange with sedimentary minerals, which may have caused the observed δ18O values (−1.12 to 4.67‰, V-SMOW). In contrast to the most vein-filling mineral phases, a breccia cement phase precipitated from a low-temperature (<50 °C) and salinity (0.0–0.4% wNaCleq) meteoric fluid. In the pores of this breccia veins, late-stage fluid migration is verified. Therefore, these veins are of paramount importance for studying the isolation properties of the rock body.

Hypozonal gold mineralization in shear zone-hosted deposits driven by fault valve action and fluid mixing: the Nalunaq deposit, Greenland

Abstract The Nalunaq deposit, Greenland, is a hypozonal, shear zone-hosted, Au deposit. The shear zone has previously been interpreted as having undergone four stages of deformation, accompanied by fluid flow and vein formation. Coupled with previous trapping T estimates, fluid inclusion data are consistent with the trapping of fluids with salinities between 28 and 45 wt% NaCl equiv., from 300 to 475°C during D 2 and D 3 , with pressure varying between c. 800 and 100 MPa. The range reflects pressure cycling during seismic slip-related depressurization events. D 4 fluids were lower salinity and trapped from 200 to 300°C, at c. 50–200 MPa during late-stage normal faulting. The variation in major element chemistry is consistent with the ingress of hypersaline, granitoid equilibrated fluids into the shear zone system and mixing with fluids that had reacted with the host metamorphic rocks. D 4 -stage fluids represent the ingress of meteoric fluids into the system. Gold contents in inclusion fluids range from c. 300 to 10 mg kg −1 . These data are consistent with the high- P–T solubility of Au as AuHS(H 2 S) 3 0 complexes, and Au deposition by decompression and cooling. The high salinities also suggest Au transport as chloride complexes may have been possible. Gold distribution was modified by the release of chemically bound or nanoscale Au during sulfide oxidation at the D 4 stage.

Pyrite geochemistry and its implications on Au-Cu skarn metallogeny: An example from the Jiguanzui deposit, Eastern China

Abstract Trace element geochemistry of pyrite is widely used to monitor ore-forming processes of various types of deposits, but its application to skarn mineral systems is not well constrained due to the multi-stage nature and complex associated mineral assemblages for skarn-type pyrite. The Jiguanzui skarn Au-Cu deposit in the Middle-Lower Yangtze River Valley Metallogenic Belt (Eastern China) is characterized by abundant pyrite that formed in the main-ore (Py1), late-ore (Py2), and post-ore (Py3) stages, which makes it ideal for unraveling skarn ore-fluid evolution. Specifically, Py1 is composed of quartz–pyrite (Py1a), quartz–calcite–pyrite (Py1b), quartz–sericite–pyrite (Py1c), quartz–chlorite±epidote–pyrite (Py1d), and quartz–K-feldspar–pyrite (Py1e), among which Py1a is the most widespread. Py2 comprises calcite–pyrite (Py2a) and calcite–K-feldspar–pyrite (Py2b), and Py3 comprise bird’s-eye pyrite (Py3a) and fingerprint-like pyrite (Py3b). The varying Co/Ni ratios (mostly &amp;gt;2) and coexistence with hydrothermal minerals (quartz, calcite, K-feldspar, chlorite, and epidote) reveal the hydrothermal origin of Py1 and Py2. The Co/Ni (0.97–7.30), Cu/Ni (8.94–186), and As/Ni (0.80–11.7) ratios, and the high trace-element contents indicate that Py3a may have been genetically linked to the waning magmatic-hydrothermal system and increasing meteoric fluid influx. Py1 generally has higher Co-Ni-Se but lower Zn-As-Mo contents than Py2. Py1 in the orebodies also has higher Cu-Au contents than Py2, consistent with the formation of Py1 during the main Au-Cu ore stage. During the ore-fluid evolution, meteoric water input and abundant galena formation in the late-ore calcite-sulfide stage may have controlled the decreasing Se-Co-Ni contents from Py1 to Py2, while the fluid cooling and pH rise (caused by acidic fluid-carbonate rock reactions) may have increased the As-Zn-Mo contents from Py1 to Py2. Py1a in the orebodies has higher As-Ag-Te, but lower Co-Ni-Se contents than Py1a in the wallrocks. The decompression and phase separation (fluid boiling) by extensive hydraulic fracturing may have caused the higher temperature, pH, and fO2 for the Py1a-forming fluids in the orebodies (than those in the wallrocks). Such fluid physicochemical differences may have been the main controlling factor on trace element spatial variations of Py1a. More importantly, the spatial variation of these trace elements in Py1a provides insights for using pyrite trace element geochemistry in skarn mineral exploration.

Hydrochemical impact of a mantle plume recorded by petrology, geochemistry, and U[sbnd]Pb geochronology of a calcite vein within the Ottawa-Bonnechere graben, Ontario, Canada

Petrology, geochemistry, fluid inclusions and UPb dating of a wide (30 cm) calcite vein in Upper Ordovician (Sandbian) limestone characterize a hydrochemical microcosm of changing fluid sources and carbon pathways related to burial, then uplift during the Phanerozoic along the Ottawa-Bonnechere graben, central Canada. UPb dating of the host limestone produces an age younger than its chronostratigraphic age suggesting the impact of diagenesis, otherwise well-defined petographically. An interred calcite fragment dated as Cambrian may highlight a platform source in this part of the graben hitherto unrecognized stratigraphically. The vein was initiated with extension across a high-angle narrow (2 cm) fault gouge allowing incursion of hot (80–125 °C) basin-derived (Mg, Ca)-Cl2 brine recorded by a saddle dolomite–dedolomite–calcite succession, not isotopically datable. Microbial methanogenesis occurred in initial narrow structural recesses giving way to recycled sedimentary bicarbonate with fracture widening. The oldest datable vein calcite (122 ± 5 Ma) consists of microcrystalline geopetal cumulates of vadose meteoric origin demarcating renewed carbonate formation following a period of near-surface alteration, dissolution, and microfracturing of the prior vein calcite during uplift. Initial 207Pb/206Pb ratios are consistent with average crust (0.819 ± 0.003), and δ18O signatures identify a meteoric signature similar to the host rock. Subsequent interlayering of isopachous calcite and pyrite, with an age of 105 ± 3 Ma for the calcite, defines onset of a meteoric phreatic environment. The role of microbial sulphate reduction is characterized isotopically. Initial 207Pb/206Pb ratios scatter below the crustal average (0.84–0.76) that, along with a meteoric δ18O signature, suggest incursion of a new fluid reservoir. A subsequent Sr, Mn, Ba-bearing–magnesium calcite marks the beginning of sustained phreatic meteoric dilution for the remaining vein history. Stable (C, O) isotopes document varying temperature and bicarbonate mixtures of sedimentary and bacterial (sulphate reduction) origins associated with a meteoric fluid. This calcite has a mean age of 94 ± 2 Ma and displays the widest range of initial 207Pb/206Pb ratios, which scatter down to 0.65. Stable and radiogenic isotopic compositions suggest a meteoric setting largely influenced by a crustal fluid reservoir of long residence time and-or transport resulting in leaching of radiogenic minerals. The final vein calcite, also of meteoric origin, has an 87Sr/86Sr ratio similar to that of the initial basin brine, yet with 13C signatures that characterize a source of oxidized methane. UTh series analysis delimits an age older than 0.5 Ma. This stage of vein calcite likely arises through meteoric fracking of Ordovician source rocks during continued basin inversion. In summary, initial brine influx followed by a shallow-crustal meteoric realm document structurally focused fluid migration with and following early Mesozoic graben exhumation. The phreatic meteoric regime of Early Cretaceous age spans a ~ 20 Ma period coincident with transient magmatism arising from near passage of the Great Meteor Hotspot. Regional paleohydrology appears to have been influenced for ~10 Ma after plume passage.

Fluid circulation in the South Tibetan Detachment System: Evidence from fluid inclusions and oxygen isotope data of quartz veins in the Ramba Dome, North Himalayan Gneiss Domes

Detachment faults are sites of intensive fluid–rock interactions. Here, we report fluid inclusion and oxygen isotope data for quartz veins in the Ramba Dome in the North Himalayan Gneiss Domes, with an aim to constrain the origin and circulation of crustal fluids associated with the South Tibetan Detachment System (STDS). Microthermometric data for fluid inclusions in quartz indicate that the fluids were aqueous and CO2 − H2O ± CH4 ± N2‐bearing with low to moderate salinities (0.60–11.80 wt% eq. NaCl). The entrapment conditions are 295–410°C and 98–135 Mpa, indicating a forming‐depth of 8–10 km. Oxygen isotopic compositions (δ18O) of quartz measured in situ by secondary ion mass spectrometry and bulk by the BrF5 method show limited variations in individual quartz veins, but δ18Oquartz values vary from 12.07 to 18.16‰ (V‐SMOW) among veins. The corresponding δ18Ofluid values range from 7.71 to 13.80‰, based on equilibrium temperatures obtained from fluid inclusions. From the footwall to the detachment zone, δ18Ofluid values exhibit a broadly decreasing trend and indicate that the STDS dominated the fluid flux pathway in the crust, with more contributions of meteoric water in the detachment zone. We further quantified the contribution of meteoric fluids to 8–27% using a binary end‐member mixing model. These data imply that the fluids were predominantly metamorphic/magmatic in origin, and were mixed with infiltrating, isotopically light, meteoric water during extensional detachment shearing of the STDS. The meteoric water can infiltrate from the surface to 8–10 km depth.

Isotopic exchange of oxygen, sulfur, hydrogen and copper between aqueous phase and the copper minerals brochantite, libethenite and olivenite

AbstractFractionation factors for the isotopes of O, H, S, or Cu (as appropriate) were determined for the minerals brochantite [Cu4(SO4)(OH)6], libethenite [Cu2(PO4)(OH)] and olivenite [Cu2(AsO4)(OH)] and corresponding aqueous solutions at temperatures between 30 and 70°C. All samples used for this determination were synthetic and the degree of fractionation was expressed as 1000 ln α = (A × 106/T2) + B, where A and B are empirical parameters. A few natural libethenite samples from its type locality Ľubietová-Podlipa were also analysed and compared to the prediction based on the isotopic composition of meteoric water and our fractionation factors. The hydrogen fractionation factors agreed with the prediction well, whereas those for oxygen did not. A possible explanation is the disequilibrium of aqueous phosphate (and also arsenate) species and the solution in our experiments or the interaction of meteoric fluids with the isotopically heavy (in terms of oxygen) country rocks. Because the effects of isotopic disequilibrium in our experiments cannot be ruled out, the oxygen fractionation factors should be used with caution. The determined fractionation factors can be used as an isotope geothermometer, given that it can be proven that the phases of interest precipitated from the same fluid in equilibrium. Libethenite is predicted to have slightly lower δ65Cu values than its parental solution, but brochantite slightly higher δ65Cu values than its parental solution. Simple forward models, simulating neutralisation or reduction of mine drainage, show that precipitation of these minerals and removal of the co-existing fluid, could cause isotopic variations (in δ65Cu) on the order of 1‰ or more.

Fluid evolution of the Zhunuo porphyry Cu-Mo deposit in Gangdese Tract, Tibet, China: A fluid-inclusion investigation

The Zhunuo porphyry Cu-Mo deposit in the western part of south Gangdese porphyry copper belt (GPCB), Tibet, is a large porphyry system. The Cu-Mo mineralization of this deposit is mainly associated with a weakly aluminous I-type Miocene granite porphyry pluton that formed in a post-collisional extensional tectonic setting. Field observations and petrographic studies demonstrate that emplacement of the pluton took place in several intrusive pulses, each with associated hydrothermal activities. Early hydrothermal alteration produced a potassic assemblage, overprinted by later phyllic alteration. At least three main stages of mineralization have been identified: (1) early A stage quartz + K-feldspar + minor sulfide veins; (2) middle stage B1-subtype veins composed of quartz + molybdenite + sporadic sulfide and B2-subtype quartz + pyrite + chalcopyrite veins; and (3) late stage pyrite + quartz D veins.Three types of fluid inclusions (FIs) in quartz were identified in the early and middle stages (i.e., CO2 bearing-aqueous vapor (V)-type and liquid (L)-type, and solid (S)-type); only aqueous L-type FIs were observed in the late stage minerals. S-type FIs contain variable solid particles, including halite, calcite, anhydrite (or gypsum), and chalcopyrite, hematite, and an unidentified transparent crystal. Only halite was dissolved during heating. Halite-bearing S-type FIs were mainly homogenized by halite dissolution at 300–470°C (S2-type), corresponding to salinities of 38.9–56.3 wt% NaCl equiv.; and minor halite bearing S-type FIs were homogenized to liquid at 360–520°C via vapor disappearance (S1-type), with salinities of 31.9–56.7 wt% NaCl equiv. Other FIs in minerals of A, B1, B2 and D veins were homogenized at temperatures of 350–550°C, 303–500°C, 305–460°C, and 250–347°C with salinities of 3.4–20.9, 2.6–22.4, 4.8–21.8, and 4.7–18.2 wt% NaCl equiv., respectively. These data suggest that the ore fluids forming the Zhunuo deposit changed from high-temperature, low-moderate salinity, CO2-bearing magmatic fluids to low-temperature, low-salinity and CO2-poor meteoric fluids. Phase separation and cooling caused the precipitation of the abundant chalcopyrite in the middle stage B2-subtype veins. The molybdenite mineralization was caused mainly by the decrease of pressure due to the release of CO2, and by phase separation of fluid in the middle stage as recorded in the B2-subtype veins. This hydrothermal ore-forming system is different from other magmatic-hydrothermal systems in GPCB, but is similar to the typical Cu-Mo porphyry systems, which were initially CO2-bearing as indicated by the presence of abundant CO2-bearing, low-moderate salinity FIs and calcite-bearing S-type FIs.

Variable Modes of Formation for Tonalite–Trondhjemite–Granodiorite–Diorite (TTG)-related Porphyry-type Cu ± Au Deposits in the Neoarchean Southern Abitibi Subprovince (Canada): Evidence from Petrochronology and Oxybarometry

Abstract Most known porphyry Cu ± Au deposits are associated with moderately oxidized and sulfur-rich, calc-alkaline to mildly alkalic arc-related magmas in the Phanerozoic. In contrast, sodium-enriched tonalite–trondhjemite–granodiorite–diorite (TTG) magmas predominant in the Archean are hypothesized to be unoxidized and sulfur-poor, which together preclude porphyry Cu deposit formation. Here, we test this hypothesis by interrogating the causative magmas for the ~2·7 Ga TTG-related Côté Gold, St-Jude, and Clifford porphyry-type Cu ± Au deposit settings in the Neoarchean southern Abitibi subprovince. New and previously published geochronological results constrain the age of emplacement of the causative magmas at ~2·74 Ga, ~2·70 Ga, and ~ 2·69 Ga, respectively. The dioritic and trondhjemitic magmas associated with Côté Gold and St-Jude evolved along a plagioclase-dominated fractionation trend, in contrast to amphibole-dominated fractionation for tonalitic magma at Clifford. Analyses of zircon grains from the Côté Gold, St-Jude, and Clifford igneous rocks yielded εHf(t) ± SD values of 4·5 ± 0·3, 4·2 ± 0·6, and 4·3 ± 0·4, and δ18O ± SD values of 5·40 ± 0·11 ‰, 3·91 ± 0·13 ‰, and 4·83 ± 0·12 ‰, respectively. These isotopic signatures indicate that, although these magmas are mantle-sourced with minimal crustal contamination, for the St-Jude and Clifford settings the magmas or their sources may have undergone variable alteration by heated seawater or meteoric fluids. Primary barometric minerals (i.e. zircon, amphibole, apatite, and magnetite–ilmenite) that survived variable alteration and metamorphism (up to greenschist facies) were used for estimating fO2 of the causative magmas. Estimation of magmatic fO2 values, reported relative to the fayalite–magnetite–quartz buffer as ΔFMQ, using zircon geochemistry indicates that the fO2 values of the St-Jude, Côté Gold, and Clifford magmas increase from ΔFMQ –0·3 ± 0·6 to ΔFMQ +0·8 ± 0·4 and to ΔFMQ +1·2 ± 0·4, respectively. In contrast, amphibole chemistry yielded systematically higher fO2 values of ΔFMQ +1·6 ± 0·3 and ΔFMQ +2·6 ± 0·1 for Côté Gold and Clifford, respectively, which are consistent with previous studies that indicate that amphibole may overestimate the fO2 of intrusive rocks by up to 1 log unit. Micro X-ray absorption near edge structure (μ-XANES) spectrometric determination of sulfur (i.e. S6+/ΣS) in primary apatite yielded ≥ΔFMQ −0·3 and ΔFMQ +1·4–1·8 for St-Jude and Clifford, respectively. The magnetite–ilmenite mineral pairs from the Clifford tonalite yielded ΔFMQ +3·3 ± 1·3 at equilibrium temperatures of 634 ± 21 °C, recording the redox state of the late stage of magma crystallization. Electron probe microanalyses revealed that apatite grains from Clifford are enriched in S (up to 0·1 wt%) relative to those of Côté Gold and St-Jude (below the detection limit), which is attributed to either relatively oxidized or sulfur-rich features of the Clifford tonalite. We interpret these results to indicate that the deposits at Côté Gold and Clifford formed from mildly (~ΔFMQ +0·8 ± 0·4) to moderately (~ΔFMQ +1·5) oxidized magmas where voluminous early sulfide saturation was probably limited, whereas the St-Jude deposit represents a rare case whereby the ingress of externally derived hydrothermal fluids facilitated metal fertility in a relatively reduced magma chamber (~ΔFMQ +0). Furthermore, we conclude that variable modes of formation for these deposits and, in addition, the apparent rarity of porphyry-type Cu–Au deposits in the Archean may be attributed to either local restriction of favorable metallogenic conditions, and/or preservation, or an exploration bias.

Genesis of the Baimadong carbonate-hosted uranium deposit, Guizhou, SW China: Constrains from geology, fluid inclusions, and C-O isotopes

The Baimadong uranium deposit is situated in the Yangtze Craton, SW China, and is one of the most representative carbonate-hosted uranium deposits in China. Uranium mineralization has spatial and genetical relationships with black and red alterations that has been documented by previous studies. However, the signature, source, and evaluation of ore-forming fluids producing the alterations and mineralization remain poorly understood. Fluid inclusions hosted in different generations of hydrothermal calcite have been analyzed in this study, including Cal 1 (pre-ore stage), Cal 2 (early ore stage), and Cal 3 (main ore stage). Three types of fluid inclusions were identified: liquid-dominated biphase, vapor-dominated biphase, and vapor-only monophase. Based on fluid inclusion microthermometry using the FIA method, the fluids associated with Cal 2 are characterized by relatively higher temperature (∼243 ℃) and salinity (5.3 wt% NaCl equiv.) compared with fluids associated with Cal 1 (Th = ∼221 ℃; Salinity = 1.9 wt% NaCl equiv.) and Cal 3 (Th = ∼144 ℃; Salinity = 2.5 wt% NaCl equiv.). The results of stable isotopes (C, O, and S) indicate that the carbon in pre-ore stage fluids was dominantly originated from host marine carbonate rocks (δ13Cfluid-PDB = −3.0 to 0.5 ‰; δ18Ofluid-SMOW = 4.8 to 11.3 ‰), the carbon and sulfur in early ore-forming fluids were mainly derived from the Niutitang Formation with minor from deep crust (δ13Cfluid-PDB = −11.2 to −8.4 ‰; δ18Ofluid-SMOW = 7.9 to 11.4 ‰; δ34Sv-CDT = −11.3 to + 2.1 ‰), whereas the main ore-forming fluids were sourced from meteoric fluids (δ13Cfluid-PDB = −8.6 to −4.9 ‰; δ18Ofluid-SMOW = 0.4 to 8.6 ‰). These results reveal that redox reaction as well as fluid-rock reaction are key factors controlling the large-scale uranium mineralization at Baimadong. Combined with these observations, geological setting, and previous geochemical features, we suggest that tectonic system together with overprinting zone of black and red alterations are indicators for exploration of carbonate-hosted uranium deposit in South China and elsewhere worldwide.

Sources of the eruption of Kambalny volcano (Southern Kamchatka) in March 2017 inferred from local earthquake tomography

Kambalny is the southernmost volcano in the Kamchatka Peninsula. After a long repose stage, on March 24, 2017, it produced a strong phreatic eruption, which ejected an ash cloud to the distance of up to 1000 km. In summer 2018, we deployed ten seismic stations in the vicinity of Kambalny for one year. Data from this network and the only permanent station located at ~20 km from the volcano provided arrival times of P and S waves for this study. We used them to localize earthquakes and obtain the 3D distributions of velocities of the P (Vp) and S waves (Vs), also mapping the Vp/Vs ratio down to a depth of ~10 km. We identify an anomaly of high Vp/Vs ratio in the depth interval of 7–10 km, and interpret it as a magma reservoir responsible for Holocene activity of Kambalny. This reservoir appears to be connected with the volcano edifice by a linear zone of high Vp/Vs ratio, which may represent a system of fractures originated during the eruption in March 2017 and served as a pathway for magma ascent. We propose that the interaction of hot magma with meteoric fluids in shallow layers caused active boiling and steam formation in a closed reservoir below the volcano. After exceeding a critical pressure, the steam escaped to the surface causing an explosive eruption. We also found evidence that geothermal fields located to the north and northwest of Kambalny might be fed from separate deep sources.

Hydrothermal activity along a strike-slip fault zone and host units in the São Francisco Craton, Brazil – Implications for fluid flow in sedimentary basins

This study combines multiscale analyses of geological, fault, fracture, and stable isotope data to investigate strike-slip deformation and channeling of hydrothermal fluids along the Cafarnaum fault and calcite veins at different distances from the fault, which is a structure in the São Francisco Craton, northeastern Brazil. Meteoric fluids with δD values near −45‰ and δ18O values near −6.5‰ and temperatures at 40–70 °C precipitated as calcite veins in the host carbonate units. The Cafarnaum fault, a N-S-striking vertical, ~170 km long fault zone, juxtaposes Neoproterozoic carbonate rocks in the western block and Mesoproterozoic siliciclastic rocks in the eastern block. A zone of restraining bends occurs at the central part of the fault, whereas termination zones of horsetail geometry occur at both ends of the Cafarnaum fault. These zones are marked by NW-SE-striking extensional faults that are oblique to the main N-S-striking fault zone, where hydrothermal deposits occur. The zone of influence of the Cafarnaum fault is ~ 20 km wide around the main fault. The fault formed during the Brasiliano orogeny (740–560 Ma) after Neoproterozoic carbonate platform deposition. In contrast with the host units, fluids along the fault zone originated in deeper levels of the crust and show much lower δ18O values, indicating higher crystallization temperatures. These fluids caused brecciation in the Neoproterozoic carbonate host rocks, whereas a subsequent decrease in fluid pressure and cooling near the surface resulted in the precipitation of a hydrothermal paragenesis in veins, also affecting the host rock.

Multiple fluid flow events from salt‐related rifting to basin inversion (Upper Pedraforca thrust sheet, SE Pyrenees)

AbstractFluid systems in inverted rifted margins are challenging to interpret because fractures formed before compression were often reactivated acting as fluid pathways as new ones formed. Deciphering the fracture and fluid flow history in such complex settings has key implications for the prediction of the distribution of mineral resources. As an example, we reconstruct the fluid flow evolution of a portion of the inverted Pyrenean rift, the Upper Pedraforca thrust sheet, from the Mesozoic extension to the Alpine orogeny. We combine structural analysis and petrographic, geochemical and geochronological data obtained from 87 samples of fracture‐filling carbonate cements. During the Late Jurassic‐Early Cretaceous, low‐temperature seawater produced dolomitization of Jurassic and Lower Cretaceous limestones in an extensional setting. During the Early Cretaceous salt‐related extension, formation waters, probably evolved seawater or fluids that interacted with Triassic evaporites, at temperatures from 125 to 149°C migrated through fractures. The formation of breccias within post‐salt rocks in primary weld zones facilitated the upward migration of formation waters that interacted with pre‐salt rocks with high 87Sr/86Sr ratios. Formation waters at temperatures of 80°C migrated during the emplacement of the Upper Pedraforca thrust sheet in the Late Cretaceous‐Palaeocene. These fluids interacted with Upper Cretaceous Carbonates and/or Triassic evaporites. In contrast, the influence of meteoric fluids increased in shallower positions due to the exhumation of the SE Pyrenees during the Eocene‐Oligocene. Coevally, hot dolomitizing fluids migrated along diapir walls during the formation of secondary welds. Supergene ores documented in diapiric areas worldwide related to meteoric fluids, and the similar meteoric percolation occurred in the Upper Pedraforca thrust sheet, suggest that supergene mineralization could be found in the Pyrenees. Brecciation of rocks in primary weld zones and evaporite detachments, where mineralization accumulate in fractures from basement‐derived fluids, also suggests that similar ores could be found in the Pyrenees.

Geometallurgical ore characterization of the high-grade polymetallic unconformity-related uranium deposit

ABSTRACT Cigar Lake is a polymetallic, unconformity-related uranium deposit with complex geochemistry and mineralogy located in the eastern Athabasca Basin of northern Saskatchewan, Canada. Variable concentrations and spatial distributions of elements of concern, such as As, Mo, Ni, Co, Se, and Zr, associated with the high-grade tetravalent uranium ores [UO2+x; U(SiO4)1–x(OH)4x] present unique mining, metallurgical, and environmental challenges. Sulfide and arsenide minerals have significant control over As, Mo, Ni, Co, and Se abundances and have properties that affect element of concern mobility, thus requiring consideration during mineral processing, mine-effluent water treatment, and long-term tailings management. The U-bearing (uraninite, coffinite) and metallic arsenide (nickeline, often called “niccolite” in the past), sulfarsenide (gersdorffite, cobaltite), and sulfide (chalcopyrite, pyrite, galena, bornite, chalcocite, sphalerite, pyrrhotite) minerals provide the main controls on the distributions of the elements of concern. Arsenic, Ni, and Co occur primarily in a reduced state as 1:1 molar ratio, Ni-Co:As, arsenide, and sulfarsenide minerals such as gersdorffite, nickeline, and cobaltite. Molybdenum occurs within molybdenite and uraninite. Selenium occurs within coffinite, sulfide, and sulfarsenide minerals. Zirconium is found within detrital zircon and coffinite. The spatial distribution and paragenesis of U-, As-, and S-bearing minerals are a result of the elemental composition, pH, and redox conditions of early formational and later meteoric fluids that formed and have modified the deposit through access along lithostratigraphic permeability and tectonic structures. Using the holistic geometallurgical paradigm presented here, the geochemistry and mineral chemistry at Cigar Lake can be used to optimize and reduce risk during long-term mine and mill planning.

Mineralogy and petrogenesis of fracture coatings in Athabasca Group sandstones from the McArthur River uranium deposit

ABSTRACT The McArthur River unconformity-related uranium deposit, located in the Athabasca Basin of Saskatchewan, Canada, is structurally hosted near the unconformity between Archean to Paleoproterozoic metasedimentary basement and the Proterozoic Athabasca Group sandstones. In this study, the mineralogy and geochemistry of fracture materials within the entire ca. 550 m thickness of the Athabasca Group sandstones and the metasedimentary (host) rocks from the McArthur River area were used to determine the paragenetic sequence and origin of minerals in and near the fractures. Our work sought to determine if the host minerals record elements associated with the uranium deposit at depth and if they could be used to guide exploration (vectoring). Fracture orientations indicate that most are moderately dipping (&amp;lt;50°) and provided permeable pathways for fluid movement within the basin, from below, and through the overlying sedimentary rocks. Many of the fractures and adjacent wall rocks record evidence of multiple distinct fluid events. Seven types of fracture fillings were identified from drill core intersecting the Athabasca Basin and present distinct colors, mineralogy, and chemical features. Brown (Type 1) and pink (Type 7) fractures host paragenetically late botryoidal goethite, Mn oxide minerals, and poorly crystallized kaolinite that formed from relatively recent low-temperature meteoric fluids, as indicated by poor crystallinity and low δ2H values of –198 to –115‰. These minerals variably replaced higher temperature minerals that are rarely preserved on the fractures or in wall rock near the fractures. Hydrothermal alteration associated with the mineralizing system at ca. 200 °C is recorded in assemblages of dickite, well-crystallized kaolinite, and spherulitic dravite in some white and yellow (Type 2) and white (Type 3) fractures, as reflected by the crystal habits and variable δ2H values of –85 to –44‰. Fibrous goethite in white and yellow (Type 2) and black and orange (Type 5) fractures and microfibrous Mn oxy-hydroxide minerals in black (Type 4) fractures also crystallized from hydrothermal fluids, but at temperatures less than 200 °C. White and yellow fractures (Type 2) containing fibrous goethite reflect fracture networks indicative of hydrothermal fluids associated with the mineralizing system during primary dispersion of pathfinder elements and therefore extend the deposit footprint. Brown (Type 1) and pink (Type 7) fractures have low δ2H values in botryoidal goethite and poorly crystallized kaolinite and are indicative of the movement of meteoric waters. Secondary dispersion of elements from the deposit to the surface on some fractures is evidence that fractures are pathways for element migration from the deposit to the surface, over distances exceeding ∼500 m.

Isotope-Geochemical Features of Apoultrabasic Metasomatites of the Sayan–Baikal Folded Area

Abstract —The paper is concerned with a geochemical study of apoultrabasic metasomatites of the Ospa–Kitoi, Parama, and Ust’-Kelyana ophiolite massifs located in the southern folded framing of the Siberian craton. The isotope (O, C, H, Sr, and Rb) systems of dunites, serpentinites, nephrites, listvenites, and talc–carbonate rocks are studied. The isotopic composition of oxygen in olivines from dunites is characterized by δ18O = 4.6–5.5‰. The δ18O values of serpentinites (4.67–7.35‰) point to the mantle genesis of fluids and might have been inherited from ultrabasic rocks. Nephrites are slightly enriched in heavy oxygen isotope (δ18O = 6.13–9.54‰). This indicates that their fluid phase was transported from serpentinites and captured a small portion of the crustal component. The widest variations in δ18O values, from 8.12 to 17.46‰, are observed in minerals from listvenites. Carbonates from these rocks show a highly heterogeneous isotopic composition of oxygen (δ18O = 12.9–18.8‰) and carbon δ13C = –2.8 to +2.8‰). These rocks formed with the contribution of metamorphogenic fluids. According to the isotopic composition of hydrogen, the examined serpentinites are divided into two groups: with δD values specific to “magmatic water” (δD = –73.50 to –85.00‰) and those typical of meteoric fluids (δD = –151.90 to –167.20‰). The listvenites are characterized by low Rb and high Sr contents. Their 87Sr/86Sr values (0.70702–0.70971) indicate the contribution of a crustal source. The study of fluid inclusions in minerals from listvenites has shown that the rocks formed under relatively low-temperature conditions. The homogenization temperatures of fluid inclusions in quartz and magnesite from listvenites of the Ospa–Kitoi massif are 184–290 ºC and 122–182 ºC, respectively. In the Parama massif, the homogenization temperature of fluid inclusions in quartz is 130–170 ºC. The solutions that formed listvenites of the Ospa–Kitoi massif were slightly saline (TDS = 2.9–8.4 wt.% NaCl eq.), with NaCl and Na2CO3 being the main salt components.