Migration of brines in the basement rocks of the Athabasca Basin through microfracture networks (P-Patch U deposit,Canada)

The unconformity-type uranium deposits of the Athabasca Basin (Saskatchewan, Canada) are hosted near the unconformity between a middle Proterozoic intracratonic sedimentary basin and an Archean to Paleo-Proterozoic metamorphic and plutonic basement. These deposits, which are considered to be the richest U deposits in the world, are the result of massive basinal fluid migrations in the basement rocks.This study shows that basinal brines have strongly penetrated into the basement not only through faults and major pathways but also by way of dense networks of microfractures which favoured the percolation of fluids down to considerable depths (hundred metres below the unconformity) and their chemical modification (salinity increase) by interaction with basement lithologies. These processes are one of the major causes of uranium mobility within the basement rocks and the formation of unconformity-type mineralization.Microfracture networks, which opened during the basinal brine stage (ca. 1600–1400 Ma) are interpreted as sets of mode I cracks corresponding to a specific stage of deformation and occur as fluid inclusion planes after healing. The stress field at that stage (σ₁ = N130–150 °E, subvertical) partly reopened the earlier microcrack networks (σ₁ = N80–110 °E and N130–150 °E, subvertical) issued from the Trans-Hudson Orogeny late retrograde metamorphic stage (ca. 1795–1720 Ma). The circulation of the two types of fluids (carbonic and brines) occurs thus at two distinct events (Trans-Hudson Orogeny late retrograde metamorphism for carbonic fluids and maximal burial diagenesis for brines) but the same main microfissure geometry was used by the fluids. This demonstrates the existence of a similar stress field direction acting before and after the basin formation. Moreover, the brine circulations in the basement acted in a wider volume than the clay-rich alteration halo surrounding the U-ores, generally considered as the main envelope of fluid percolation outside the fault systems. The data on the chemistry of the fluids and on the geometry of their migration at various scales emphasise the fundamental role of the basement in the chemical evolution of highly saline brines linked to unconformity-related uranium mineralization in the Athabasca Basin.     

Percolation of diagenetic fluids in the Archaean basement of the Franceville basin

The Palaeoproterozoic Franceville basin, Gabon, is mainly known for its high-grade uranium deposits, which are the only ones known to act as natural nuclear fission reactors. Previous work in the Kiéné region investigated the nature of the fluids responsible for these natural nuclear reactors. The present work focuses on the top of the Archaean granitic basement, specifically, to identify and date the successive alteration events that affected this basement just below the unconformity separating it from the Palaeoproterozoic basin. Core from four drill holes crosscutting the basin–basement unconformity have been studied. Dating is based on U–Pb isotopic analyses performed on monazite. The origin of fluids is discussed from the study of fluid inclusion planes (FIP) in quartz from basement granitoids. From the deepest part of the drill holes to the unconformable boundary with the basin, propylitic alteration assemblages are progressively replaced by illite and locally by a phengite + Fe chlorite ± Fe oxide assemblage. Illitic alteration is particularly strong along the sediment–granitoid contact and is associated with quartz dissolution. It was followed by calcite and anhydrite precipitation as fracture fillings. U–Pb isotopic dating outlines three successive events: a 3.0–2.9-Ga primary magmatic event, a 2.6-Ga propylitic alteration and a late 1.9-Ga diagenetic event. Fluid inclusion microthermometry suggests the circulation of three types of fluids: (1) a Na–Ca-rich diagenetic brine, (2) a moderately saline (diagenetic + meteoric) fluid, and (3) a low-salinity fluid of probable meteoric origin. These fluids are similar to those previously identified within the overlying sedimentary rocks of the Franceville basin. Overall, the data collected in this study show that the Proterozoic–Archaean unconformity has operated as a major flow corridor for fluids circulation, around 1.9 Ga.     

Fluid compositions and P-T conditions of vein-type uranium mineralization in the Beaverlodge uranium district,northern Saskatchewan,Canada

The Beaverlodge district in northern Saskatchewan is known for “vein-type” uranium mineralization. Most of the uranium deposits are spatially related to major structures, and hosted by ca. 3.2–1.9 Ga granitic rocks (and albitite derived from them) and by ca. 2.33 Ga Murmac Bay Group amphibolite, all of which are unconformably overlain locally by deformed but unmetamorphosed redbeds of the ca. 1.82 Ga Martin Group, and by the flat-lying ca. 1.75–1.5 Ga Athabasca Group. The uranium mineralization is mainly hosted in fault rocks (breccias) and carbonate ± quartz ± albite veins, referred to as breccia-style and vein-style mineralization, respectively, with the latter being the focus of this study. Most of the mineralized veins occur in the basement rocks, although some crosscut the Martin Group. This study examines the field, petrographic, fluid inclusion and C-O isotope characteristics of mineralized and non-mineralized veins from 19 deposits/occurrences as well as from the Martin Group, with an aim to better understand the mineralizing environment and processes.The coexistence of liquid-dominated (L + V), vapour-dominated (V + L) and vapour-only (V) fluid inclusions within individual fluid inclusion assemblages (FIAs) in the veins suggests fluid immiscibility and heterogeneous trapping. The L + V inclusions with the lowest homogenization temperatures (T_h) within individual FIAs are interpreted to represent homogeneous trapping of the liquid phase, which yield T_h values from 78° to 330 °C (mainly 100° to 250 °C), and salinities from 0.2 to 30.8 wt.% NaCl equivalent. Mass spectrometric analysis of bulk fluid inclusions shows that the volatiles are dominated by H₂O (average 97.2 mol%), with minor amounts of CO₂, CH₄, H₂, O₂, N₂, Ar and He. Fluid pressures were estimated to be < 200 bars based on the inference of fluid immiscibility, fluid temperatures of 100° to 250 °C, and low concentrations of non-aqueous volatiles (< 3 mol%). The δ¹⁸O_VPDB and δ¹³C_VPDB of carbonate minerals associated with mineralization range from − 20.5 to − 8.9‰ and − 10.1 to − 0.9‰, respectively. The δ¹⁸O_VSMOW values of the parent fluids calculated using the T_h values range from − 9.6 to + 17.0‰, with the majority from 0 to + 5.0‰. O isotopes of paired equilibrium quartz and calcite, analyzed by secondary ion mass spectrometry (SIMS), yield temperatures from 161° to 248 °C, which are consistent with the fluid inclusion data.The new fluid inclusion and stable isotope data are inconsistent with a metamorphic or magmatic-hydrothermal model as proposed in some previous studies (for breccia-style and vein-style mineralization), but rather support a model in which the vein-type uranium mineralization took place at relatively low temperature (100° to 250 °C) and shallow (< 2 km) conditions, with fluid pressure fluctuating between hydrostatic and sub-hydrostatic regimes, possibly related to episodic faulting. The mineralizing fluids were mainly sourced from the Martin Lake Basin, and uraninite was precipitated as a result of mixing between this basin-derived fluid and fluids carrying reducing agents (Fe^2 +, CH₄) derived from the basement, although fluid-rock reactions and fluid immiscibility may have also played a role.     

Spatial–temporal evolution of ore-forming fluids and related mineralization in the western Lanping basin,Yunnan Province,China

The Lanping basin is a significant Pb–Zn–Cu–Ag mineralization belt in the Sanjiang Tethyan metallogenic province. A series of sediment-hosted Himalayan Cu–Ag–Pb–Zn polymetallic deposits have been discovered in the western part of the basin, controlled by a thrust–nappe system. In the thrust–nappe system, the Cu orebodies mainly occur in the western and relatively deep part of the mineralization system (the root zone), whereas the Pb–Zn–Ag (± Cu) orebodies occur in the eastern and relatively shallow part of the system (the front zone), both as vein-type mineralization.In this paper we present new data, combined with existing data on fluid inclusions, isotopes and geologic characteristics of representative deposits, to provide the first study that contrasts mineralizing fluids in the Cu–Ag (Mo) and Pb–Zn–Ag (Cu) polymetallic deposits.Fluid inclusion and isotope studies show that the Cu–Ag (Mo) mineralization in the root zone formed predominantly from deep crustal fluids, with the participation of basinal brines. The deep crustal fluids are marked by high CO₂ content, relatively high temperatures (280 to 340 °C) and low salinities (1 to 4 wt.% NaCl equivalent), whereas the basinal brine shows relatively low temperatures (160 °C to 220 °C) and high salinities (12 to 22 wt.% NaCl equivalent), containing almost no CO₂. In comparison, hydrothermal activity associated with the Pb–Zn–Ag (± Cu) deposits in the front zone is characterized by basinal brine, with relatively low temperatures (130 °C to 180 °C), high salinities (9 to 24 wt.% NaCl equivalent), and low CO₂ concentrations. Although evolved meteoric waters have predominantly been proposed as the source for deep crustal fluids, magmatic and metamorphic components cannot be completely excluded. The basinal brine was predominantly derived from meteoric water.The δ³⁴S values of sulfides from the Cu–Ag (Mo) deposits and Pb–Zn–Ag (± Cu) deposits range from − 17.9 to 16.3‰ and from 2.5 to 11.2‰, respectively. These ranges may relate to variations in physicochemical conditions or compositional variation of the sources. Lead isotope compositions indicate that the ore-forming metals were predominantly derived from sedimentary rocks of the Lanping basin.     

Intermediate sulfidation epithermal gold-base metal deposits in Tertiary subaerial volcanic rocks,Sahinli/Tespih Dere (Lapseki/Western Turkey)

Gold in the Sahinli and Tespih Dere intermediate sulfidation gold-base metal deposits in Western Turkey occurs in relatively deep epithermal quartz veins along with base metal minerals which have epithermal textures, including plumose quartz, vug infills, comb and cockade textures and matrix-supported milled breccias. The total sulfide content of the veins in the area is variable ranging from < 1% to 60% and is dominated by pyrite, galena, sphalerite and chalcopyrite. Sphalerite is Fe-poor (0.6 to 1.4 mol% FeS). Minor amounts of Ag-rich tetrahedrite are present. Primary hydrothermal alteration minerals include illite/muscovite, mixed-layer illite/smectite (11.6 Å) and clinochlore towards the east and, alunite, dickite/nacrite and pyrophyllite towards the west at Sahinli; major illite/muscovite and dickite occur at Tespih Dere and Sarioluk, respectively.Fluid inclusions in main-stage quartz at Sahinli are only liquid-rich, with homogenization temperatures ranging from 220 to 322 °C and the majority of T_h values between 250 and 300 °C. Salinity ranges from 4.3 to 6.9 wt.% NaCl equiv. First ice-melting temperatures (T_mf) between ?24.5 and ?19.0 °C indicate that the fluids were dominated by NaCl – H₂O during mineralization. The relatively higher average T_h at the Tespih Dere deposit (295 °C) is attributed to a relatively deeper level of exposure.Calculated δ¹⁸O values indicate that ore-forming hydrothermal fluids in the study area had δ¹⁸O_H2O ranging from + 1.1 to + 9.7‰ (average = 3.8‰), strongly ¹⁸O-enriched compared with present-day hydrothermal meteoric water in the area (δ¹⁸O = ?8.5‰). δD values of fluid inclusions in quartz range from ?58 to ?93‰ and δD values of clay minerals and alunite from ?40 to ?119‰. δD values from intermediate argillic alteration (average = ?68‰) in the study area are very similar to δD values of the present-day local geothermal system (average δD = ?54‰) whereas δD values from advanced-argillic alteration (average δD = ?33‰) are very different from the present-day local geothermal system.The δ³⁴S values in samples from the Sahinli and Tespih Dere deposits average ?2.9‰ for pyrite; ?3.3‰ for chalcopyrite; ?5.4‰ for sphalerite and ?7.6‰ for galena. These data are consistent with derivation of the sulfur from either igneous rocks or possibly from local wallrock.     

Hydro-geochemical and isotopic fluid evolution of the Los Azufres geothermal field,Central Mexico

Hydrothermal alteration at Los Azufres geothermal field is mostly propylitic with a progressive dehydration with depth and temperature increase. Argillic and advanced argillic zones overlie the propylitic zone owing to the activity of gases in the system. The deepest fluid inclusions (proto-fluid) are liquid-rich with low salinity, with NaCl dominant fluid type and ice melting temperatures (T_mi) near zero (0 °C), and salinities of 0.8 wt% NaCl equivalent. The homogenization temperature (T_h)  = 325 ± 5 °C. The boiling zone shows T_h = ±300 °C and apparent salinities between 1 and 4.9 wt% NaCl equivalent, implying a vaporization process and a very important participation of non-condensable gases (NCGs), mostly CO₂. Positive clathrate melting temperatures (fusion) with T_h = 150 °C are observed in the upper part of the geothermal reservoir (from 0 to 700 m depth). These could well be the evidence of a high gas concentration. The current water produced at the geothermal wells is NaCl rich (geothermal brine) and is fully equilibrated with the host rock at temperatures between T = 300 and 340 °C. The hot spring waters are acid-sulfate, indicating that they are derived from meteoric water heated by geothermal steam. The NCGs related to the steam dominant zone are composed mostly of CO₂ (80–98% of all the gases). The gases represent between 2 and 9 wt% of the total mass of the fluid of the reservoir.The authors interpret the evolution of this system as deep liquid water boiling when ascending through fractures connected to the surface. Boiling is caused by a drop of pressure, which favors an increase in the steam phase within the brine ascending towards the surface. During this ascent, the fluid becomes steam-dominant in the shallowest zone, and mixes with meteoric water in perched aquifers. Stable isotope compositions (δ¹⁸O–δD) of the geothermal brine indicate mixing between meteoric water and a minor magmatic component. The enrichment in δ¹⁸O is due to the rock–water interaction at relatively high temperatures. δ¹³C stable isotope data show a magmatic source with a minor meteoric contribution for CO₂. The initial isotopic value δ³⁴S_RES = −2.3‰, which implies a magmatic source. More negative values are observed for shallow pyrite and range from δ³⁴S (FeS₂) = −4‰ to −4.9‰, indicating boiling. The same fractionation tendencies are observed for fluids in the reservoir from results for δ¹⁸O.     

Ore-forming process of the Huijiabao gold district,southwestern Guizhou Province,China: Evidence from fluid inclusions and stable isotopes

The Huijiabao gold district is one of the major producers for Carlin-type gold deposits in southwestern Guizhou Province, China, including Taipingdong, Zimudang, Shuiyindong, Bojitian and other gold deposits/occurrences. Petrographic observation, microthermometric study and Laser Raman spectroscopy were carried out on the fluid inclusions within representative minerals in various mineralization stages from these four gold deposits. Five types of fluid inclusions have been recognized in hydrothermal minerals of different ore-forming stages: aqueous inclusions, CO₂ inclusions, CO₂–H₂O inclusions, hydrocarbon inclusions, and hydrocarbon–H₂O inclusions. The ore-forming fluids are characterized by a H₂O + CO₂ + CH₄ ± N₂ system with medium to low temperature and low salinity. From early mineralization stage to later ones, the compositions of the ore-forming fluids experienced an evolution of H₂O + NaCl → H₂O + NaCl + CO₂ + CH₄ ± N₂ → H₂O + NaCl ± CH₄ ± CO₂ with a slight decrease in homogenization temperature and salinity. The δ¹⁸O values of the main-stage quartz vary from 15.2‰ to 24.1‰, while the δD_H2O and calculated δ¹⁸O_H2O values of the ore-forming fluids range from −56.9 to −116.3‰ and from 2.12‰ to 12.7‰, respectively. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite change in the range of −9.1‰ to −0.5‰ and 11.1–23.2‰, respectively. Stable isotopic characteristics indicate that the ore-forming fluid was mainly composed of ore- and hydrocarbon-bearing basinal fluid. The dynamic fractionation of the sulfur in the diagenetic pyrite is controlled by bacterial reduction of marine sulfates. The hydrothermal sulfides and the diagenetic pyrite from the host rocks are very similar in their sulfur isotopic composition, suggesting that the sulfur in the ore-forming fluids was mainly derived from dissolution of diagenetic pyrite. The study of fluid inclusions indicates that immiscibility of H₂O–NaCl–CO₂ fluids took place during the main mineralization stage and caused the precipitation and enrichment of gold.     

Influence of crude oil on the genesis of the Lanjiagou porphyry molybdenum deposit,western Liaoning Province,China

The Lanjiagou porphyry molybdenum deposit in western Liaoning Province, China, is hosted in fine-grained Jurassic granites. LA-ICP-MS zircon U–Pb analyses indicate that the crystallization of the ore-hosting granites took place 185.0 ± 1.8 Ma (MSWD = 1.4). Molybdenum mineralization in the deposit can be divided into three stages: the stockwork quartz vein stage, the planar quartz vein stage, and the fissure-filling quartz vein stage. Re–Os isotopic ages for the molybdenite from the stockwork quartz vein-type ores yielded an isochron age of 188.8 ± 9.9 Ma (MSWD = 3.0), while six samples from the planar quartz vein-type ores yielded a similar isochron age of 185.6 ± 1.2 Ma (MSWD = 0.5). Re–Os isotopic ages for the molybdenite identical, within error, to zircon U–Pb isotopic ages indicate that the molybdenum mineralization is related to the host intrusions. Apart from primary inorganic fluid inclusions (IFIs), a large number of primary organic fluid inclusions (OFIs) are found in the latter two stages of vein quartz, and minors found in the first stage. The components and characteristics of OFIs in the three stages of vein quartz differ from each other, which is also true for the IFIs. OFIs in stockwork vein quartz are characterized by halite-bearing inclusions, and organic liquids in the inclusions are brown and do not fluoresce under ultraviolet (UV) light. Homogenization temperatures (T_h) for the primary IFIs coeval with OFIs of this stage ranges from 300 °C to > 450 °C, while the salinity varies from 10 to 53 wt.% NaCl equiv.. In planar vein quartz, OFIs are predominately two-phased (liquid and gas), and salt daughter minerals (halite) are absent. Organic liquids are light brown to colorless and show blue fluorescence under UV light; The T_h range for the IFIs of this stage is 250–360 °C, and the salinity range is 3–17 wt.% NaCl equiv. Finally, OFIs in fissure-filling vein quartz are marked by liquid–gas inclusions. Organic liquids are generally colorless and show yellow fluorescence under UV light. The T_h range for the primary IFIs is 180–240 °C and the salinity range is 4–11 wt.% NaCl equiv. Organic geochemical analyses indicate that organic matter in the Lanjiagou deposit was derived from mature crude oil. We suggest that large volumes of crude-oil-bearing non-magmatic fluids were flushed into the Lanjiagou porphyry hydrothermal system during all phases of ore formation and likely played important roles in mineralization.     

Primary to re-equilibrated fluids and geochemical signatures for the evolution of the Nagthat siliciclastics in the Tons valley,Lesser Himalaya,India

Medium to coarse-grained Neo-Proterozoic Nagthat siliciclastic rocks form a part of the Krol Formation in the Lesser Himalayan geotectonic zone. Fluid inclusion and geochemical studies have been carried out on the Nagthat siliciclastics from the Tons valley to determine their provenance during the Proterozoic and their recrystallisation during maximum burial to uplift. Fluid inclusion studies have been carried out on detrital, recrystallised quartz grains and quartz overgrowths. Major and trace element analyses of the siliciclastics, the relationships of SiO₂ with various trace elements, and the association of various trace elements with mineral species suggest a granitic source for these siliciclastics. Primary Q1 aqueous brine inclusions and Q3 H₂O–CO₂ fluid with 0.9 gm/cm³ CO₂ density in detrital quartz grains characterised the protolith of the sandstone as granite or metamorphic rocks. H₂O–NaCl fluids participated in the cementation history, temperatures of quartz overgrowth from 198 to 232 °C show the effect of maximum burial. The re-equilibration of the primary fluid due to elevated internal pressure > confining pressure is evident from features like ‘C’ shaped cavities, stretching of the inclusions, their migration, decrepitation clusters, etc. During recrystallisation these inclusions were equilibrated at 187 ° and 235 °C in a restricted fluid of aqueous, moderately saline composition. The observed inclusion morphology is attributed to a decrease in external pressure related to isothermal decompression uplift.     

Penetration of surface-evaporated brines into the Proterozoic basement and deposition of Co and Ag at Bou Azzer (Morocco): Evidence from fluid inclusions

Ag-ores occur in a specific zone of the Bou Azzer Co–As deposit in the Precambrian basement of the Anti-Atlas belt (Morocco), especially in highly microfractured quartz-depleted diorite. They formed after the main Co–As stage of mineralization, but both ore stages (Co–As and Ag-ore) appear linked to similar immiscible fluids: an hyper-saline Na–Ca brine (5.5–22 wt.%. eq. NaCl and 13.5–18.5 wt.% eq. CaCl₂, with Na/Ca ranging from 0.4 to 1.2 during Ag-mineralization) occurring as L + V ± halite fluid inclusions and CH₄–(N₂) gas dominated fluids. Pressure–temperature estimates for the Ag-stage range from 40 to 80 MPa and 150 to 200 °C e.g. at a temperature slightly lower than that of the preceding Co–As stage (200–220 °C).Chlorinity, cation (Na/Ca ca. 2.2) and halogen ratios (Cl/Br from 300 to 360) are typical of deep basinal brines, especially of surface-evaporated brines that have exceeded halite saturation. The primary brines were modified by fluid–rock interaction during burial and migration through the basement. Ag-deposition was probably favoured by dilution and cooling due to the mixing of brines with less saline fluids. Similarities between the Ag-brines from Bou Azzer, Zgounder and Imiter suggest a regional scale circulation of basinal brines during extension probably later than the Triassic, during the early stages of rifting of the Atlantic.     

Fluid inclusion evidence for hydrothermal fluid evolution in the Darreh-Zar porphyry copper deposit,Iran

The Darreh-Zar porphyry copper deposit is associated with a quartz monzonitic–granodioritic–porphyritic stock hosted by an Eocene volcanic sedimentary complex in which magmatic hydrothermal fluids were introduced and formed veins and alteration. Within the deepest quartz-rich and chalcopyrite-poor group A veins, LVHS2 inclusions trapped high salinity, high temperature aqueous fluids exsolved directly from a relatively shallow magma (0.5 kbar). These late fluids were enriched in NaCl and reached halite saturation as a result of the low pressure of magma crystallization and fluid exsolution. These fluids extracted Cu from the crystallizing melt and transported it to the hydrothermal system. As a result of ascent, the temperature and pressure of these fluids decreased from 600 to 415 °C, and approximately 500–315 bars. At these conditions, K-feldspar and biotite were stabilized. Type A veins were formed at a depth of ∼1.2 km under conditions of lithostatic pressure and abrupt cooling. Upon cooling and decompressing, the fluid intersected with the liquid–vapor field resulting in separation of immiscible liquid and vapor. This stage was recorded by formation of LVHS1, LVHS3 and VL inclusions. These immiscible fluids formed chalcopyrite–pyrite–quartz veins with sericitic alteration envelopes (B veins) under the lithostatic–hydrostatic pressure regime at temperatures between 415 and 355 °C at 1.3 km below the paleowater table. As the fluids ascended, copper contents decreased and these fluids were diluted by mixing with the low salinity-external fluid. Therefore, pyrite-dominated quartz veins were formed in purely hydrostatic conditions in which pressure decreased from 125 bars to 54 bars and temperature decreased from 355 to 298 °C. During the magmatic-hydrothermal evolution, the composition and P–T regime changed drastically and caused various types of veins and alterations. The abundance of chalcopyrite precipitation in group B veins suggests that boiling and cooling were important factors in copper mineralization in Darreh-Zar.     

Geology and fluid evolution of the Wangfeng orogenic-type gold deposit,Western Tian Shan,China

The Wangfeng gold deposit is located in Western Tian Shan and the central section of the Central Asian Orogenic Belt (CAOB). The deposit is mainly hosted in Precambrian metamorphic rocks and Caledonian granites and is structurally controlled by the Shenglidaban ductile shear zone. The gold orebodies consist of gold-bearing quartz veins and altered mylonite. The mineralization can be divided into three stages: quartz–pyrite veins in the early stage, sulfide–quartz veins in the middle stage, and quartz–carbonate veins or veinlets in the late stage. Ore minerals and native gold mainly formed in the middle stage. Four types of fluid inclusions were identified based on petrography and laser Raman spectroscopy: CO₂–H₂O inclusions (C-type), pure CO₂ inclusions (PC-type), NaCl–H₂O inclusions (W-type), and daughter mineral-bearing inclusions (S-type). The early-stage quartz contains only primary CO₂–H₂O fluid inclusions with salinities of 1.62 to 8.03 wt.% NaCl equivalent, bulk densities of 0.73 to 0.89 g/cm³, and homogenization temperatures of 256 °C–390 °C. Vapor bubbles are composed of CO₂. The middle-stage quartz contains all four types of fluid inclusions, of which the CO₂–H₂O and NaCl–H₂O types yield homogenization temperatures of 210 °C–340 °C and 230 °C–300 °C, respectively. The CO₂–H₂O fluid inclusions have salinities of 0.83 to 9.59 wt.% NaCl equivalent and bulk densities of 0.77 to 0.95 g/cm³, with vapor bubbles composed of CO₂, CH₄, and N₂. Fluid inclusions in the late-stage quartz are NaCl–H₂O solution with low salinities (0.35–3.87 wt.% NaCl equivalent) and low homogenization temperatures (122 °C–214 °C). The coexistence of inclusions of these four types in middle-stage quartz suggests that fluid boiling occurred in the middle-stage mineralization. Trapping pressures estimated from CO₂–H₂O inclusions are 110–300 MPa and 90–250 MPa for the early and middle stages, respectively, suggesting that gold mineralization mainly occurred at depths of about 10 km. In general, the Wangfeng gold deposit originated from a metamorphic fluid system characterized by low salinity, low density, and enrichment of CO₂. Depressurized fluid boiling caused gold precipitation. Given the regional geology, ore geology, fluid-inclusion features, and ore-forming age, the Wangfeng gold deposit can be classified as a hypozonal orogenic gold deposit.     

Hydrocarbon migration in the Zagros Basin,offshore Iran,for understanding the fluid flow in the Oligocene–Miocene carbonate reservoirs

Kuh-e Mond Field is a conventional heavy oil resource in the Zagros foreland Basin, Iran, produced from the fractured carbonates partially filled by dolomite, calcite, and anhydrite cement. Vitrinite reflectance data from carbonate reservoir suggest low-maturation levels corresponding to paleotemperatures as low as 50 °C. The observed maturation level (< 0.5% Rmax) does not exceed values for simple burial maturation based on the estimated burial history. Oil inclusions within fracture-filled calcite and dolomite cement indicate the key role of these fractures in oil migration.The fluid inclusion temperature profiles constructed from the available data revealed the occurrence of petroleum in dolomite, calcite, and anhydrite and characterize the distinct variations in the homogenization temperatures (T_h). Fluid inclusions in syntectonic calcite veins homogenize between 22 °C and 90 °C, showing a salinity decrease from 22 to 18 eq. wt.% NaCl. Fluid inclusions in anhydrite homogenize at < 50 °C, showing that the pore fluids became warmer and more saline during burial. The T_h range in the calcite-dolomite cement depicts a change in water composition; therefore, we infer these cements precipitated from petroleum-derived fluids. The microthermometry data on the petroleum fluid inclusions suggest that the reservoir was filled with heavy black oils and high-salinity waters and indicate that undersaturated oil was present in a hydrostatically pressured reservoir.The T_h data do not support vertical migration of hot fluids througout the section, but extensive lateral fluid migration, most likely, drove tectonically dewatering in the south or west of the pool.     

Mechanism of mineralization in the Changjiang uranium ore field,South China: Evidence from fluid inclusions,hydrothermal alteration,and H–O isotopes

The Changjiang uranium ore field, which contains >10,000 tonnes of recoverable U with a grade of 0.1–0.5%, is hosted by Triassic two-mica and Jurassic biotite granites, and is one of the most important uranium ore fields in South China. The minerals associated with alteration and mineralization can be divided into two stages, namely syn-ore and post-ore. The syn-ore minerals are primarily quartz, pitchblende, hematite, hydromica, chlorite, fluorite, and pyrite; the post-ore minerals include quartz, calcite, fluorite, pyrite, and hematite. The fluid inclusions of the early syn-ore stage characteristically contain O₂, and those of the late syn-ore and post-ore stage contain H₂ and CH₄. The fluid inclusions in quartz of the syn-ore stage include H₂O, H₂O–CO₂, and CO₂ types, and they occur in clusters or along trails. Homogenization temperatures (T_h) for the H₂O–CO₂ and two-phase H₂O inclusions range from 106 °C to >350 °C and cluster in two distinct groups for each type; salinities are lower than 10 wt% NaCl equiv. The ore-forming fluids underwent CO₂ effervescence or phase separation at ∼250 °C under a pressure of 1000–1100 bar. The U/Th values of the altered granites are lowest close to the ore, increase outwards, but subsequently decrease close to unaltered granites. From the unaltered granites to the ore, the lowest Fe₂O₃/FeO values become lower and the highest values higher. The REE patterns of the altered granites and the ores are similar to each other. The U contents of the ores show a positive correlation with total REE contents but a negative correlation with LREE/HREE ratios, indicating the pitchblende is REE-bearing and selectively HREE-rich. The δEu values of the ore show a positive correlation with U contents, indicating the early syn-ore fluids were oxidizing. The δCe values show a negative correlation, indicating the later mineralization environment became reducing. The water–rock interactions of the early syn-ore stage resulted in oxidization of altered granites and reduction of the ore-forming fluids, and it was this reduction that led to the uranium mineralization. During alteration in the early syn-ore stage, the oxidizing fluids leached uranium from granites close to faults, and Fe₂O₃/FeO ratios increased in the alteration zones. The late syn-ore and post-ore alteration decreased the Fe₂O₃/FeO ratios in the alteration zones. The δ¹⁸O_W–SMOW values of the ore-forming fluids range from −1.8‰ to 5.4‰, and the δD_W–SMOW values range from −104.4‰ to −51.6‰, suggesting meteoric water. The meteoric water underwent at least two stages of water–rock interaction: the first caused the fluids to become uranium-bearing, and the second stage, which was primarily associated with ore-bearing faults, led to uranium deposition as pitchblende, accompanied by CO₂ effervescence.     

Genesis of the Proterozoic Mangabeira tin–indium mineralization,Central Brazil: Evidence from geology,petrology, fluid inclusion and stable isotope data

The Mangabeira deposit is the only known Brazilian tin mineralization with indium. It is hosted in the Paleo- to Mesoproterozoic Mangabeira within-plate granitic massif, which has geochemical characteristics of NYF fertile granites. The granitic massif is hosted in Archean to Paleoproterozoic metasedimentary rocks (Ticunzal formation), Paleoproterozoic peraluminous granites (Aurumina suite) and a granite–gneiss complex. The mineralized area comprises evolved Li-siderophyllite granite, topaz–albite granite, Li–F-rich mica greisens and a quartz–topaz rock, similar to topazite. Two types of greisens are recognized in the mineralized area: zinnwaldite greisen and Li-rich muscovite greisen, formed by metasomatism of topaz–albite granite and Li-siderophyllite granite, respectively. Cassiterite occurs in the quartz–topaz rock and in the greisens. Indium minerals, such as roquesite (CuInS₂), yanomamite (InAsO₄·2H₂O) and dzhalindite (In(OH₃)), and In-rich cassiterite, sphalerite, stannite group minerals and scorodite are more abundant in the quartz–topaz rock, and are also recognized in albitized biotite granite and in Li-rich muscovite greisen. The host rocks and mineralized zones were subsequently overprinted by the Brasiliano orogenic event.Primary widespread two-phase aqueous and rare coeval aqueous-carbonic fluid inclusions are preserved in quartz from the topaz–albite granite, in quartz and topaz from the quartz–topaz rock and in cassiterite from the Li-rich muscovite greisen. Eutectic temperatures are − 25 °C to − 23 °C, allowing modeling of the aqueous fluids in the system H₂O–NaCl(–KCl). Rare three-phase H₂O–NaCl fluid inclusions (45–50 wt.% NaCl equiv.) are restricted to the topaz–albite granite. Salinities and homogenization temperatures of the aqueous and aqueous-carbonic fluid inclusions decrease from the topaz–albite granite (15–20 wt.% NaCl equiv.; 400 °C–450 °C), to the quartz–topaz rock (10–15 wt.% NaCl equiv.; 250 °C–350 °C) and to the greisen (0–5 wt.% NaCl equiv.; 200 °C–250 °C). Secondary fluid inclusions have the same range of salinities as the primary fluid inclusions, and homogenize between 150 and 210 °C.The estimated equilibrium temperatures based on δ¹⁸O of quartz–mica pairs are 610–680 °C for the topaz–albite granite and 285–370 °C for the Li-rich muscovite greisens. These data are coherent with measured fluid inclusion homogenization temperatures. Temperatures estimated using arsenopyrite geothermometry yield crystallization temperatures of 490–530 °C for the quartz–topaz rock and 415–505 °C for the zinnwaldite greisens. The fluids in equilibrium with the topaz–albite granite have calculated δ¹⁸O and δD values of 5.6–7.5‰ and − 67 to − 58‰, respectively. Estimated δ¹⁸O and δD values are mainly 4.8–7.9‰ and − 60 to − 30‰, respectively, for the fluids in equilibrium with the quartz–topaz rock and zinnwaldite greisen; and 3.4–3.9‰ and − 25 to − 17‰, respectively, for the Li-rich muscovite greisen fluid. δ³⁴S data on arsenopyrite from the quartz–topaz rock vary from − 1.74 to − 0.74‰, consistent with a magmatic origin for the sulfur. The integration of fluid inclusion with oxygen isotopic data allows for estimation of the minimum crystallization pressure at ca. 770 bar for the host topaz–albite granite, which is consistent with its evolved signature.Based on petrological, fluid inclusion and isotope data it is proposed that the greisens and related Mangabeira Sn–In mineralization had a similar hydrothermal genesis, which involved exsolution of F-rich, Sn–In-bearing magmatic fluids from the topaz–albite granite, early formation of the quartz–topaz rock and zinnwaldite greisen, progressive cooling and Li-rich muscovite greisen formation due to interaction with meteoric water. The quartz–topaz rock is considered to have formed in the magmatic-hydrothermal transition. The mineralizing saline and CO₂-bearing fluids are interpreted to be of magmatic origin, based on the isotopic data and paragenesis, which has been documented as characteristic of the tin mineralization genetically related to Proterozoic within-plate granitic magmatism in the Goias Tin Province, Central Brazil.     

Fluid evolution in the southern part of the Proterozoic Vazante Group,Brazil: Implications for exploration of sedimentary-hosted base metal deposits

The Proterozoic Vazante Group carbonate rocks were submitted to multiple stages of fluid circulation from diagenesis to orogenesis as documented by detailed mineralogical, fluid inclusion and isotopic studies of the Upper Morro do Pinheiro and Lower Pamplona members from the Serra do Poço Verde Formation in the southern part of the paleo-basin. These units are the main hosts for the hypogene, structurally-controlled zinc silicate deposits in the Vazante Zinc District, including the Vazante mine, which is considered to be the largest willemitic (Zn₂SiO₄) deposit in the world, with estimated total resources of 40–60 Mt at 20% Zn. Five hydrothermal alteration types were identified in the Southern Extension of the Vazante Group. (I) Early stage alteration comprises dolomite substitution bands and nodules, associated with moderate salinity H₂O-NaCl-CaCl₂ fluids, with temperatures around 90 °C, interpreted as late-diagenetic. The calculated C and O isotopic compositions of the fluids suggest meteoric and/or connate origin and interaction with organic carbon. (II) Pre-ore stage alteration is evidenced by dog-tooth dolomite and quartz with minor Fe-oxi/hydroxides which fills dissolution voids formed by H₂O-NaCl-CaCl₂ ± MgCl₂ fluids at temperatures around 100° to 150 °C. The C isotopic data also indicate interaction with organic carbon. The two first stages are poor in ore-related elements. (III) Ore stage encompasses four phases of mineral precipitation. The first is distal and characterized by red stained dolostones due to disseminated hematite and red dolomite. The second is the main phase of the ore stage, composed of massive red dolomite, massive hematite and willemite with enrichment mainly in Fe₂O₃, SiO₂, Ag, As, Cd, Cu, Ni, Pb, Se and Zn. The third phase comprises white dolomite, hematite and traces of willemite with enrichment in MnO, Cd, Ni and Pb. The calculated C and O isotopic compositions of the fluids (at 180 °C) associated with pervasive alteration yielded values heavier than the diagenetic stage and lower than the host rock. The fourth phase corresponds to Zn-chlorite and quartz which are associated with H₂O-NaCl fluids of variable salinities and distinct temperatures (90–140 °C and 170–190 °C). (IV) Pyrite-bearing vein characterized by pyrite, sphalerite, white dolomite, fine hematite and late quartz, with C and O isotopic and fluid inclusion compositions that are similar to the three phases of dolomite of the ore stage. These data suggest a co-genetic relationship of these two alteration styles. (V) The late sulfide stage characterized by rare galena-bearing stringers with sphalerite, chalcocite, greenockite, covellite and white dolomite that cross-cut the main ore stage phases. The ore-related fluid compositions associated with the silicate zinc mineralization in the southern part of the Vazante Group are also similar to the fluids reported in previous work for the sulfide zinc-lead deposits in the northern part, indicating favorable conditions for metal transport during the Brasiliano Orogeny. Sulfide ore would have precipitated in zones where sulfur was available and silicate zinc in structures where mineralizing fluids interacted with evolved meteoric water. This finding implies that carbonate sequences in other districts with sulfide lead-zinc deposits may also host hypogene silicate zinc deposits.     

Fluid types and their genetic meaning for the BIF-hosted iron ores,Krivoy Rog,Ukraine

This paper contributes to the understanding of the genesis of epigenetic, hypogene BIF-hosted iron deposits situated in the eastern part of Ukrainian Shield. It presents new data from the Krivoy Rog iron mining district (Skelevatske–Magnetitove deposit, Frunze underground mine and Balka Severnaya Krasnaya outcrop) and focuses on the investigation of ore genesis through application of fluid inclusion petrography, microthermometry, Raman spectroscopy and baro-acoustic decrepitation of fluid inclusions. The study investigates inclusions preserved in quartz and magnetite associated with the low-grade iron ores (31–37% Fe) and iron-rich quartzites (38–45% Fe) of the Saksaganskaya Suite, as well as magnetite from the locally named high-grade iron ores (52–56% Fe). These high-grade ores resulted from alteration of iron quartzites in the Saksaganskiy thrust footwall (Saksaganskiy tectonic block) and were a precursor to supergene martite, high-grade ores (60–70% Fe). Based on the new data two stages of iron ore formation (metamorphic and metasomatic) are proposed.The metamorphic stage, resulting in formation of quartz veins within the low-grade iron ore and iron-rich quartzites, involved fluids of four different compositions: CO₂-rich, H₂O, H₂O–CO₂(± N₂–CH₄)–NaCl(± NaHCO₃) and H₂O–CO₂(± N₂–CH₄)–NaCl. The salinities of these fluids were relatively low (up to 7 mass% NaCl equiv.) as these fluids were derived from dehydration and decarbonation of the BIF rocks, however the origin of the nahcolite (NaHCO₃) remains unresolved. The minimum P–T conditions for the formation of these veins, inferred from microthermometry are T_min = 219–246 °C and P_min = 130–158 MPa. The baro-acoustic decrepitation analyses of magnetite bands indicated that the low-grade iron ore from the Skelevatske–Magnetitove deposit was metamorphosed at T = ~ 530 °C.The metasomatic stage post-dated and partially overlapped the metamorphic stage and led to the upgrade of iron quartzites to the high-grade iron ores. The genesis of these ores, which are located in the Saksaganskiy tectonic block (Saksaganskiy ore field), and the factors controlling iron ore-forming processes are highly controversial. According to the study of quartz-hosted fluid inclusions from the thrust zone the metasomatic stage involved at least three different episodes of the fluid flow, simultaneous with thrusting and deformation. During the 1^st episode three types of fluids were introduced: CO₂–CH₄–N₂(± C), CO₂(± N₂–CH₄) and low salinity H₂O–N₂–CH₄–NaCl (6.38–7.1 mass% NaCl equiv.). The 2^nd episode included expulsion of the aqueous fluids H₂O–N₂–CH₄–NaCl(± CO₂, ± C) of moderate salinities (15.22–16.76 mass% NaCl equiv.), whereas the 3^rd event involved high salinity fluids H₂O–NaCl(± C) (20–35 mass% NaCl equiv.). The fluids most probably interacted with country rocks (e.g. schists) supplying them with CH₄ and N₂. The high salinity fluids were most likely either magmatic–hydrothermal fluids derived from the Saksaganskiy igneous body or heated basinal brines, and they may have caused pervasive leaching of Fe from metavolcanic and/or the BIF rocks. The baro-acoustic decrepitation analyses of magnetite comprising the high-grade iron ore showed formation T = ~ 430–500 °C. The fluid inclusion data suggest that the upgrade to high-grade Fe ores might be a result of the Krivoy Rog BIF alteration by multiple flows of structurally controlled, metamorphic and magmatic–hydrothermal fluids or heated basinal brines.     

Age and origin of uranium mineralization in the Camie River deposit (Otish Basin,Québec,Canada)

The Camie River uranium deposit is located in the southeastern part of the Paleoproterozoic Otish Basin (Québec). The uranium mineralization consists of disseminated and vein uraninite and brannerite precipitated close to the unconformity between Paleoproterozoic fluviatile, pervasively altered, sandstones and conglomerates of the Matoush Formation and the underlying sulfide-bearing graphitic schists of the Archean Hippocampe greenstone belt. Diagenetic orange/pink feldspathic alteration of the Matoush Formation consists of authigenic albite cement partly replaced by later orthoclase cement, with the Na₂O content of clastic rocks increasing with depth. Basin-wide green muscovite alteration affected both the Matoush Formation and the top of the basement Tichegami Group. Uraninite with minor brannerite is mainly hosted by subvertical reverse faults in basement graphitic metapelites ± sulfides and overlying sandstones and conglomerates. Uranium mineralization is associated with chlorite veins and alteration with temperatures near 320 °C, that are paragenetically late relative to the diagenetic feldspathic and muscovite alterations. Re-Os geochronology of molybdenite intergrown with uraninite yields an age of 1724.0 ± 4.9 Ma, whereas uraninite yields an identical, although slightly discordant, 1724 ± 29 Ma SIMS U-Pb age. Uraninite has high concentrations in REE with flat REE spectra resembling those of uraninite formed from metamorphic fluids, rather than the bell-shaped patterns typical of unconformity-related uraninite. Paragenesis and geochronology therefore show that the uranium mineralization formed approximately 440 million years after intrusion of the Otish Gabbro dykes and sills at ∼2176 Ma, which constrains the minimum age for the sedimentary host rocks. The post-diagenetic stage of uraninite after feldspathic and muscovite alterations, the paragenetic sequence and the brannerite-uraninite assemblage, the relatively high temperature for the mineralizing event (∼320 °C) following the diagenetic Na- and K-dominated alteration, lack of evidence for brines typical of unconformity-related U deposits, the older age of the Otish Basin compared to worldwide basins hosting unconformity-related uranium deposits, the large age difference between basin fill and mineralization, the older age of the uranium oxide compared to ages for worldwide unconformity-related U deposits, and the flat REE spectra of uraninite do not support the previous interpretation that the Camie River deposit is an unconformity-associated uranium deposit. Rather, the evidence is more consistent with a PaleoProterozoic, higher-temperature hydrothermal event at 1724 Ma, whose origin remains speculative.     

Metallogeny of the Shilu Fe–Co–Cu deposit,Hainan Island,South China: Constraints from fluid inclusions and stable isotopes

The Shilu deposit is a world-class Fe–Co–Cu orebody located in the Changjiang area of the western part of Hainan Island, South China. The distribution of Fe, Co, and Cu orebodies is controlled by strata of the No. 6 Formation in the Shilu Group and the Beiyi synclinorium. Based on a petrological study of the host rocks and their alteration assemblages, and textural and structural features of the ores, four mineralization stages have been identified: (1) the sedimentary ore-forming period; (2) the metamorphic ore-forming period; (3) the hydrothermal mineralization comprising the skarn and quartz–sulfide stage; and (4) the supergene period. The fluid inclusions in sedimentary quartz and/or chert indicate low temperatures (ca. 160 °C) and low salinities from 0.7 to 3.1 wt.% NaCl_eq, which corresponds to densities of 0.77 to 0.93 g/cm³. CO₂-bearing or carbonic inclusions have been interpreted to result from regional metamorphism. Homogenization temperatures of fluid inclusions for the skarn stage have a wide range from 148 °C to 497 °C and the salinities of the fluid inclusions range from 1.2 to 22.3 wt.% NaCl_eq, which corresponds to densities from 0.56 to 0.94 g/cm³. Fluid inclusions of the quartz–sulfide stage yield homogenization temperatures of 151–356 °C and salinities from 0.9 to 8.1 wt.% NaCl_eq, which equates to fluid densities from 0.63 to 0.96 g/cm³.Sulfur isotopic compositions indicate that sulfur of the sedimentary anhydrite and Co-bearing pyrite, and the quartz–sulfide stage, was derived from seawater sulfate and thermochemical sulfate reduction of dissolved anhydrite at temperatures of 200 °C and 300 °C, respectively. H and O isotopic compositions of the skarn and quartz–sulfide stage demonstrate that the ore-forming fluids were largely derived from magmatic water, with minor inputs from metamorphic or meteoric water. The Shilu iron ore deposit has an exhalative sedimentary origin, but has been overprinted by regional deformation and metamorphism. The Shilu Co–Cu deposit has a hydrothermal origin and is temporally and genetically associated with Indosinian granitoid rocks.     

Relationships among sedimentology, stratigraphy, and diagenesis in the Proterozoic Thelon Basin, Nunavut, Canada: implications for paleoaquifers and sedimentary-hosted mineral deposits

The Thelon Basin, Nunavut, Canada, is host to unconformity-type uranium mineralisation and has the potential to host other economic deposits. The Thelon Formation (ca. 1750 Ma) is composed of thick (meters to tens of meters), poorly sorted, trough cross-bedded conglomerate and coarse-grained lithic arenite beds, and to a lesser extent, well-sorted, medium- to coarse-grained quartz arenite beds. Relatively rare, 1–12 cm thick, clay-rich siltstones to fine-grained sandstone layers punctuate the coarser lithofacies. Based on regional analysis of drill cores and outcrops, multiple unconformity-bounded sequences are defined in this fluvial-dominated sedimentary succession. Stratigraphic correlations are based on detailed lithofacies analysis, distinct changes in fining-upward cycle thickness, and intraformational surfaces (unconformities, transgressive surfaces, and paleosols).Diagenetic and paragenetic relationships vary systematically with sedimentology and stratigraphy of the Thelon and provide a framework for understanding the evolution of fluid-flow systems in the context of basin hydrostratigraphy. Stratigraphic units with well-sorted textures, which lacked clay and unstable framework grains, originally were aquifers (depositional aquifers) during early basin evolution. However, pervasive, early quartz cementation radically reduced the porosity and permeability of these units, occluding pore throats and transforming them into aquitards. Proximal fluvial and alluvial fan lithofacies that contained detrital, mechanically infiltrated, and diagenetic clay minerals and/or unstable detrital grains originally had low permeabilities and only experienced minor quartz cementation. In the deep burial setting (2–7 km), these units retained sufficient permeability to allow diagenetic fluid flow (diagenetic aquifers) as suggested by feldspar dissolution, quartz dissolution, and formation and recrystallization of illite and other diagenetic reactions. Tracing potential diagenetic aquifer and aquitard units across the study area allowed development of a hydrostratigraphic model. In this model, diagenetic aquifers onlap onto, and focused basinal fluids into basement rocks to the east in the Thelon Basin (in the vicinity of the Kiggavik uranium deposit).