Metamorphic fluid origins in the Osborne Fe oxide–Cu–Au deposit,Australia: evidence from noble gases and halogens

The Osborne iron oxide–copper–gold (IOCG) deposit is hosted by amphibolite facies metasedimentary rocks and associated with pegmatite sheets formed by anatexis during peak metamorphism. Eleven samples of ore-related hydrothermal quartz and two pegmatitic quartz–feldspar samples contain similarly complex fluid inclusion assemblages that include variably saline (<12–65 wt% salts) aqueous and liquid carbon dioxide varieties that are typical of IOCG mineralisation. The diverse fluid inclusion types present in each of these different samples have been investigated by neutron-activated noble gas analysis using a combination of semi-selective thermal and mechanical decrepitation techniques. Ore-related quartz contains aqueous and carbonic fluid inclusions that have similar ⁴⁰Ar/³⁶Ar values of between 300 and 2,200. The highest-salinity fluid inclusions (47–65 wt% salts) have calculated ³⁶Ar concentrations of approximately 1–5 ppb, which are more variable than air-saturated water (ASW = 1.3–2.7 ppb). These fluid inclusions have extremely variable Br/Cl values of between 3.8 × 10⁻³ and 0.3 × 10⁻³, and I/Cl values of between 27 × 10⁻⁶ and 2.4 × 10⁻⁶ (all ratios are molar). Fluid inclusions in the two pegmatite samples have similar ⁴⁰Ar/³⁶Ar values of ≤1,700 and an overlapping range of Br/Cl and I/Cl values. High-salinity fluid inclusions in the pegmatite samples have 2.5–21 ppb ³⁶Ar, that overlap the range determined for ore-related samples in only one case. The fluid inclusions in both sample groups have ⁸⁴Kr/³⁶Ar and ¹²⁹Xe/³⁶Ar ratios that are mainly in the range of air and air-saturated water and are similar to mid-crustal rocks and fluids from other settings. The uniformly low ⁴⁰Ar/³⁶Ar values (<2,200) and extremely variable Br/Cl and I/Cl values do not favour a singular or dominant fluid origin from basement- or mantle-derived magmatic fluids related to A-type magmatism. Instead, the data are compatible with the involvement of metamorphic fluids that have interacted with anatectic melts to variable extents. The ‘metamorphic’ fluids probably represent a mixture of (1) inherited sedimentary pore fluids and (2) locally derived metamorphic volatilisation products. The lowest Br/Cl and I/Cl values and the ultra-high salinities are most easily explained by the dissolution of evaporites. The data demonstrate that externally derived magmatic fluids are not a ubiquitous component of IOCG ore-forming systems, but are compatible with models in which IOCG mineralisation is localised at sites of mixing between fluids of different origin. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorised users.     

Halogens and noble gases in sedimentary formation waters and Zn–Pb deposits: A case study from the Lennard Shelf,Australia

Halogen ratios (Br/Cl and I/Cl) and concentrations provide important information about how sedimentary formation waters acquire their salinity, but the possible influence of organic Br derived from sedimentary wall-rocks is rarely quantified. Here, it is demonstrated that Br/Cl versus I/Cl mixing diagrams can be used to deconvolve organic Br contributions; that organic matter has a limited range of Br/I ratios; and that organic Br is a more significant component in Zn–Pb deposit ore fluids than previously recognised. The significance of these findings is illustrated for the Lennard Shelf Zn–Pb deposits of Western Australia.Fluid inclusions related to Lennard Shelf Zn–Pb mineralisation have variable salinity and hydrocarbon contents. The halogen data from these fluid inclusions require mixing of three fluid end-members: (1) an evaporated seawater bittern brine (30 wt.% NaCl equiv.) with greater than seawater Br/Cl ratio; (2) a lower salinity pore fluid (?5 wt.% NaCl equiv.) with moderately elevated Br/Cl and I/Cl; and (3) fluids with Br/Cl ratios of ～5 times seawater and extremely elevated I/Cl ratios of ～11,500 times seawater. The first two fluids have ⁴⁰Ar/³⁶Ar of 300–400 and greater than air saturated water ³⁶Ar concentrations that are typical of fluid inclusions related to Zn–Pb mineralisation. The third ‘organic-rich’ fluid has the highest ⁴⁰Ar/³⁶Ar ratio of up to 1500 and a depleted ³⁶Ar concentration.Mineralisation is interpreted to have resulted from mixing of Zn-rich evaporitic brines and H₂S present in hydrocarbons. It is suggested that aqueous fluids acquired organic Br and I from hydrocarbons, and that hydrocarbons exsolving from the aqueous fluid removed noble gases from solution. Interaction of variably saline brines and hydrocarbons could account for the variable Br/Cl and I/Cl composition, and ³⁶Ar concentrations, recorded by Lennard Shelf fluid inclusions. The distinct ⁴⁰Ar/³⁶Ar signature of the fluid with the highest I/Cl ratio suggests the hydrocarbons and brines were sourced independently from different parts of the sedimentary basin. These data indicate the complementary nature of halogen and noble gas analysis and provide new constraints on important mixing processes during sediment-hosted Zn–Pb mineralisation.     

Mixed messages in iron oxide–copper–gold systems of the Cloncurry district,Australia: insights from PIXE analysis of halogens and copper in fluid inclusions

Proterozoic rocks of the Cloncurry district in NW Queensland, Australia, are host to giant (tens to hundreds of square kilometers) hydrothermal systems that include (1) barren regional sodic–calcic alteration, (2) granite-hosted hydrothermal complexes with magmatic–hydrothermal transition features, and (3) iron oxide–copper–gold (IOCG) deposits. Fluid inclusion microthermometry and proton-induced X-ray emission (PIXE) show that IOCG deposits and the granite-hosted hydrothermal complexes contain abundant high temperature, ultrasaline, complex multisolid (type 1) inclusions that are less common in the regional sodic–calcic alteration. The latter is characterized by lower salinity three-phase halite-bearing (type 2) and two-phase (type 3) aqueous inclusions. Copper contents of the type 1 inclusions (>300 ppm) is higher than in type 2 and 3 inclusions (<300 ppm), and the highest copper concentrations (>1,000 ppm) are found both in the granite-hosted systems and in inclusions with Br/Cl ratios that are consistent with a magmatic source. The Br/Cl ratios of the inclusions with lower Cu contents are consistent with an evaporite-related origin. Wide ranges in salinity and homogenization temperatures for fluid inclusions in IOCG deposits and evidence for multiple fluid sources, as suggested by halogen ratios, indicate fluid mixing as an important process in IOCG genesis. The data support both leaching of Cu by voluminous nonmagmatic fluids from crustal rocks, as well as the direct exsolution of Cu-rich fluids from magmas. However, larger IOCG deposits may form from magmatic-derived fluids based on their higher Cu content.     

Part I. Decrepitation and degassing behaviour of quartz up to 1560 °C: Analysis of noble gases and halogens in complex fluid inclusion assemblages

Stepped heating and crushing experiments have been used to investigate the noble gas and halogen degassing behaviour of quartz in detail. Samples with diverse character were selected from the Eloise and Osborne, Iron Oxide Copper Gold (IOCG) ore deposits, and the Railway Fault, 13 km south of the Mt Isa Mine, in the Proterozoic Mt Isa Inlier of northeast Australia. Quartz has been shown to have a bimodal degassing profile. The first degassing mode at temperatures of <700 °C is caused by thermally induced mechanical decrepitation of fluid inclusions. Changes in the Br/Cl, I/Cl, Ar/Cl and ⁴⁰Ar/³⁶Ar composition of gas released at different temperatures up to 700 °C can be related to the decrepitation of different types of fluid inclusion observed by microthermometry. These variations with temperature permit deconvolution of the complex fluid inclusion assemblages associated with the IOCG samples; the ultra high salinity, multi solid (MS) and liquid-vapour-daughter (LVD) fluid inclusions, with a predominantly primary origin, decrepitate at higher temperatures than lower salinity liquid-vapour (LV) and monophase (M) fluid inclusions that have a predominantly secondary origin. Three of the IOCG samples have primary MS and LVD fluid inclusions characterized by molar Br/Cl values of between 0.25 × 10⁻³ and 0.66 × 10⁻³, I/Cl between 0.37 × 10⁻⁶ and 5.0 × 10⁻⁶, ⁴⁰Ar/³⁶Ar values of <1000 and low ³⁶Ar concentrations of 0.7-1.0 × 10⁻⁶ cm³ cm⁻³H₂O. These low values are most easily explained by the involvement of halite dissolution water in IOCG genesis. One of the IOCG samples has Br/Cl of 1.3-2.0 × 10⁻³ and I/Cl of 10 × 10⁻⁶, similar to juvenile magmatic fluids in Phanerozoic Porphyry Copper Deposits. This sample also has a higher ³⁶Ar concentration of 3.5 × 10⁻⁶ cm³ cm⁻³H₂O and a slightly elevated ⁴⁰Ar/³⁶Ar of 2236. Step heating reveals limited and non-systematic variation within the more homogenous population of LV fluid inclusions from the Railway Fault. The samples have mean values of 8.1 × 10⁻³ for Br/Cl; 9.4-12 × 10⁻⁶ for I/Cl; <2000 for ⁴⁰Ar/³⁶Ar; and 4.7-4.8 × 10⁻⁶ cm³ cm⁻³H₂O for ³⁶Ar concentration. The Br/Cl values are similar to those previously reported for basinal brines present in silicic alteration at the Mt Isa Mine and the additional data can be explained by interaction of such a bittern brine with fine grained sedimentary rocks in the sub-surface. The second mode of quartz degassing occurs between 1200 and 1450 °C and releases a greater volume of gas than the first degassing mode. Several lines of evidence, including microscope observations, indicate that the gas released at high temperature is also from the fluid inclusion reservoir. However, its release may be triggered by a metastable phase transition of quartz (∼1200 °C) and caution is required in interpretation of the fluid compositions obtained at these temperatures. The data provide an improved understanding of fluid inclusion decrepitation behaviour that is different to that obtained in lower temperatures experiments designed by other workers to investigate H-isotope fractionation.     

Origin of Ore-Forming Fluids of Mississippi Valley-Type （MVT） Pb-Zn Deposits in Kangdian Area, China

Analyses of fluid-inclusion leachates from ore deposits show that Na/Br ratios are within the range of 75 - 358 and Cl/Br 67 - 394, respectively, and this variation trend coincides with the seawater evaporation trajectory on the basis of the Na/Br and Cl/Br ratios. The average Cl/Br and Na/Br ratios of mineralizing fluids are 185 and 173 respectively, which are very close to the ratios ( 120 and 233 ) of the residual evaporated seawater past the point of halite precipitation. It is suggested that the original mineralizing brine was derived from highly evapo-rated seawater with a high salinity. However, the inclusion fluids have absolute Na values of 69.9—2606.2 mmol kg^-1 and Cl values of 106.7 — 1995.5 mmol kg^-1. Most of the values are much less than those of seawater: Na, 485 mmol kg^-1 and Cl, 566 mmol kg^-1 , respectively; the salinity measured from fluid inclusions of the deposits ranges from 2.47 wt% to 15.78 wt% NaCl equiv. The mineralizing brine has been diluted. The δ ^18O and δD values of ore-forming fluids vary from -8.21‰ to 9.51‰ and from -40.3‰ to -94.3‰, respectively. The δD values of meteoric water in this region varied from - 80‰ to - 100‰ during the Jurassic. This evidenced that the ore-forming fluids are the mixture of seawater and meteoric water. Highly evaporated seawater was responsible for leaching and extracting Pb, Zn and Fe, and mixed with and diluted by descending meteoric water, which resulted in the formation of ores.     

Helium and argon isotopic compositions of the Longquanzhan gold deposit in the Yishu fault zone and their geological implications

The Longquanzhan gold deposit hosted in granitic cataclasites with mylontization of the foot wall of the main Yishui-Tangtou fault. 3He/4He ratios in fluid inclusions range from 0. 14 to 0. 24 R/Ra,close to those of the crust-source helium. 40Ar/36Ar ratios were measured to be 289-1811, slightly higher than those of atmospheric argon. The results of analysis of helium and argon isotopes suggested that ore-forming fluids were derived chiefly from the crust. The δ18O values of fluid inclusions from vein quartz range from -1.78‰ to 4.07‰, and the δD values of the fluid inclusions vary between -74‰ and -77‰. The hydrogen and oxygen isotope data indicated that the ore-forming fluid for the Longquanzhan gold deposit had mixed with meteoric water in the process of mineralization. This is consistent with the conclusion from the helium and argon isotope data.     

Fluid origin and structural enhancement during mineralization of the Jinshan orogenic gold deposit, South China

The Jinshan orogenic gold deposit is a world-class deposit hosted by a ductile shear zone caused by a transpressional terrane collision during Neoproterozoic time. Ore bodies at the deposit include laminated quartz veins and disseminated pyrite-bearing mylonite. Most quartz veins in the shear zone, with and without gold mineralization, were boudinaged during progressive shear deformation with three generations of boudinage structures produced at different stages of progressive deformation. Observations of ore-controlling structures at various scales indicate syn-deformational mineralization. Fluid inclusions from pyrite intergrown with auriferous quartz have ³He/⁴He ratios of 0.15–0.24 Ra and ⁴⁰Ar/³⁶Ar ratios 575–3,060. δ¹⁸O_fluid values calculated from quartz are 5.5–8.4‰, and δD values of fluid inclusions contained in quartz range between −61‰ and −75‰. The δ¹³C values of ankerite range from −5.0‰ to −4.2‰, and ankerite δ¹⁸O values from 4.4‰ to 8.0‰. The noble gas and stable isotope data suggest a predominant crustal source of ore fluids with less than 5% mantle component. Data also show that in situ fluids were generated locally by pervasive pressure solution, and that widespread dissolution seams acted as pathways of fluid flow, migration, and precipitation. The in situ fluids and fluids derived from deeper levels of the crust were focused by deformation and deformation structures at various scales through solution-dissolution creep, crack-seal slip, and cyclic fault-valve mechanisms during progressively localized deformation and gold mineralization.     

Fluid inclusion characteristics of mesothermal gold deposits in the Xiaoqinling district, Shaanxi and Henan Provinces, People's Republic of China

Fluid inclusions were studied in quartz samples from early (stage I) gold-poor quartz veins and later (stage II) gold- and sulphide-rich quartz veins from the Wenyu, Dongchuang, Qiangma, and Guijiayu mesothermal gold deposits in the Xiaoqinling district, China. Fluid inclusion petrography, microthermometry, and bulk gas analyses show remarkably consistent fluid composition in all studied deposits. Primary inclusions in quartz samples are dominated by mixed CO₂-H₂O inclusions, which have a wide range in CO₂ content and coexist with lesser primary CO₂-rich and aqueous inclusions. In addition, a few secondary aqueous inclusions are found along late-healed fractures. Microthermometry and bulk gas analyses suggest hydrothermal fluids with typically 15–30 mol% CO₂ in stage I inclusions and 10–20 mol% CO₂ in stage II inclusions. Estimates of fluid salinity decrease from 7.4–9.2 equivalent wt.% NaCl to 5.7–7.4 equivalent wt.% NaCl between stage I and II. Primary aqueous inclusions in both stages show consistent salinity with, but slightly lower Th _total than, their coexistent CO₂-H₂O inclusions. The coexisting CO₂-rich, CO₂-H₂O, and primary aqueous inclusions in both stage I and II quartz are interpreted to have been trapped during unmixing of a homogeneous CO₂-H₂O parent fluid. The homogenisation temperatures of the primary aqueous inclusions give an estimate of trapping temperature of the fluids. Trapping conditions are typically 300–370 °C and 2.2 kbar for stage I fluids and 250–320 °C and 1.6 kbar for stage II fluids. The CO₂-H₂O stage I and II fluids are probably from a magmatic source, most likely devolatilizing Cretaceous Yanshanian granitoids. The study demonstrates that gold is largely deposited as pressures and temperatures fall accompanying fluid immiscibility in stage II veins. Received: 15 May 1997 / Accepted: 10 June 1998     

Noble gas and halogen evidence for the origin of Scandinavian sandstone-hosted Pb-Zn deposits

Fluid origins in the sandstone-hosted Pb-Zn class of ore deposit have been investigated in three deposits from Scandinavia; Laisvall, Vassbo and Osen. The deposits studied are hosted by autochthonous Cambrian sandstones that preserve a near original structural relationship to the underlying Precambrian basement, enabling the role of basement interaction to be assessed.Mineral samples have been collected from across the paragenetic sequence: sphalerite, galena, pyrite, fluorite and barite, of impregnation and related joint-hosted mineralization. Fluid-inclusion halogen (Cl, Br and I) and noble gas isotope (⁴⁰Ar, ³⁶Ar, ⁸⁴Kr) compositions were determined simultaneously by noble gas mass spectrometry of irradiated sample splits. Complementary He isotope analyses are obtained from nonirradiated splits of the same samples.³He/⁴He values at Laisvall and Osen are highly radiogenic, 0.02 Ra, and the ⁴He/⁴⁰Ar* ratio extends to values greater than the crustal production value of 5, characteristic of low-temperature crustal fluids. At Vassbo, a slightly elevated ³He/⁴He ratio of 0.1-0.3 Ra is compatible with a very minor mantle component (1%-4%) suggesting a distal source for the basinal brine-dominated fluid.Br/Cl molar ratios 3.2-8.2 × 10⁻³ are greater than the present seawater value of 1.54 × 10⁻³ and correspond with I/Cl molar ratios in the range 64-1600 × 10⁻⁶. The upper limits of both the I/Cl and Br/Cl values are amongst the highest measured in crustal fluids. Together, the data indicate acquisition of salinity by the evaporation of seawater beyond the point of halite saturation and subsequent fluid interaction with I-rich organic matter in the subsurface. The data are compatible with the independent transport of sulfate and sulfide and indicate that fluids responsible for joint-hosted mineralization were distinct to those responsible for impregnation mineralization.All three deposits preserve fluids with ⁴⁰Ar/³⁶Ar in the range of 6,000-10,000 and fluid inclusion ⁴⁰Ar* concentrations of >0.02-0.05 cm³cm⁻³. Fluid-inclusion ⁴He concentrations are also extremely elevated with maximum values of ∼0.1 cm³cm⁻³ in Laisvall fluorite and sphalerite. The high ⁴⁰Ar/³⁶Ar values, together with the high ⁴He and ⁴⁰Ar* concentrations, result from a very long premineralization crustal residence time on the order of 100-200 Ma.Together, the noble gas and halogen data are compatible with a Caledonian mineralization event (∼425 Ma) caused by mixing of two or more, long-lived, hydrothermal basinal brines and pore fluids at the sites of mineralization. The data suggest negligible recharge of the basinal brines by meteoric water and indicate extensive fluid-basement interaction before mineralization. The similar noble gas composition of each deposit, suggests that similar processes operated at all three deposits and favors a single-pass fluid-flow model for mineralization.     

Composition and origin of fluids associated with lode gold deposits in a Mesoarchean greenstone belt (Warrawoona Syncline, Pilbara Craton, Western Australia) using synchrotron radiation X-ray fluorescence

Microthermometry and Raman spectroscopy techniques are routinely use to constrain ore-fluids δ¹⁸O and molar proportions of anhydrous gas species (CO₂, CH₄, N₂). However, these methods remain imprecise concerning the ore-fluids composition and source. Synchrotron radiation X-ray fluorescence allows access to major and trace element concentrations (Cl, Br and K, Ca, Fe, Cu, Zn, As, Rb, Sr) of single fluid inclusion. In this paper, we present the results of the combination of these routine and newly developed techniques in order to document the fluids composition and source associated with a Mesoarchaean lode gold deposit (Warrawoona Syncline, Western Australia). Fluid inclusion analyses show that quartz veins preserved records of three fluid inclusion populations. Early fluids inclusions, related to quartz veins precipitation, are characterized by a moderate to high Br/Cl ratio relative to modern seawater, CO₂ ± CH₄ ± N₂, low to moderate salinities and significant base metal (Fe, Cu, Zn) and metalloid (As) concentrations. Late fluid inclusions trapped in secondary aqueous fluid inclusions are divided into two populations with distinct compositions. The first population consists of moderately saline aqueous brines, with a Br/Cl ratio close to modern seawater and a low concentration of base metals and metalloids. The second population is a fluid of low to moderate salinity, with a low Br/Cl ratio relative to modern seawater and significant enrichment in Fe, Zn, Sr and Rb. These three fluid inclusion populations point to three contrasting sources: (1) a carbonic fluid of mixed metamorphic and magmatic origin associated with the gold-bearing quartz precipitation; (2) a secondary aqueous fluid with seawater affinity; and (3) a surface-derived secondary aqueous fluid modified through interaction with felsic lithologies, before being flushed into the syncline. Primary carbonic fluids present similar characteristics than those ascribed to Mesoarchaean lode gold deposits. This suggests similar mineralization processes for mid- and Mesoarchaean lode gold deposits despite contrasting fluid–rock interaction histories. However, in regard to the protracted history documented in the Warrawoona Syncline, we question the robustness of the epigenetic crustal continuum model, as ore-fluid characteristics equally support an epigenetic or a polyphased mineralization process.     

Fluid inclusion noble gas and halogen evidence on the origin of Cu-Porphyry mineralising fluids

The naturally occurring noble gas isotopes (⁴⁰Ar, ³⁶Ar, ⁸⁴Kr and ¹²⁹Xe) and halogens (Cl, Br, I) have been determined simultaneously in irradiated quartz vein samples by noble gas mass spectrometry. Quartz vein samples were collected from the potassic and propylitic alteration zones of six porphyry copper deposits (PCD): Bingham Canyon, Utah; and Silverbell, Ray, Mission, Pinto Valley and Globe-Miami in Arizona. In addition, analyses of ³He/⁴He have been obtained from sulphide minerals hosted by the quartz veins at Silverbell, Ray, Pinto Valley and Globe-Miami.The majority of PCD fluids studied have Br/Cl and I/Cl ratios that overlap those of fluids included in mantle diamond, suggesting that the salinity had a juvenile origin. The high I/Cl (121 × 10⁻⁶ mole, M) in samples from the propylitic zone of Silverbell is attributed to the presence of sedimentary formation water.³He/⁴He ratios have R/Ra values in the range 0.3 to 1.72, and provide evidence for the involvement of a crustal component in addition to mantle volatiles. ⁴⁰Ar/³⁶Ar ratios vary from meteoric values of ∼317 in the propylitic zone of Bingham Canyon, and 323 in the skarn alteration of Mission up to 3225 in the potassic zone of Pinto Valley. Fluids in both the potassic and propylitic alteration zones of every deposit are a mixture of a low salinity end-member comprising meteoric water and air, and a high salinity end-member consisting of a mixed mantle and crustal fluid.The ⁴⁰Ar/Cl ratio of fluid inclusions at Pinto Valley (∼10⁻⁴ M) is similar to values obtained previously for mantle fluids. The ⁴⁰Ar/Cl value is two orders of magnitude lower at Bingham Canyon, where a depleted ³⁶Ar concentration (0.2 × 10⁻⁶ cm³/g) below that of air saturated water (ASW), and a range of highly fractionated noble gas compositions (F⁸⁴Kr = 13 and F¹²⁹Xe = 160) indicate that boiling and pulsed fluid flow have occurred.     

Hydrocarbon- and ore-bearing basinal fluids: a possible link between gold mineralization and hydrocarbon accumulation in the Youjiang basin,South China

The Youjiang basin, which flanks the southwest edge of the Yangtze craton in South China, contains many Carlin-type gold deposits and abundant paleo-oil reservoirs. The gold deposits and paleo-oil reservoirs are restricted to the same tectonic units, commonly at the basinal margins and within the intrabasinal isolated platforms and/or bioherms. The gold deposits are hosted by Permian to Triassic carbonate and siliciclastic rocks that typically contain high contents of organic carbon. Paragenetic relationships indicate that most of the deposits exhibit an early stage of barren quartz ± pyrite (stage I), a main stage of auriferous quartz + arsenian pyrite + arsenopyrite + marcasite (stage II), and a late stage of quartz + calcite + realgar ± orpiment ± native arsenic ± stibnite ± cinnabar ± dolomite (stage III). Bitumen in the gold deposits is commonly present as a migrated hydrocarbon product in mineralized host rocks, particularly close to high grade ores, but is absent in barren sedimentary rocks. Bitumen dispersed in the mineralized rocks is closely associated and/or intergrown with the main stage jasperoidal quartz, arsenian pyrite, and arsenopyrite. Bitumen occurring in hydrothermal veins and veinlets is paragenetically associated with stages II and III mineral assemblages. These observations suggest an intimate relationship between bitumen precipitation and gold mineralization. In the paleo-petroleum reservoirs that typically occur in Permian reef limestones, bitumen is most commonly observed in open spaces, either alone or associated with calcite. Where bitumen occurs with calcite, it is typically concentrated along pore/vein centers as well as along the wall of pores and fractures, indicating approximately coeval precipitation. In the gold deposits, aqueous fluid inclusions are dominant in the early stage barren quartz veins (stage I), with a homogenization temperature range typically of 230°C to 270°C and a salinity range of 2.6 to 7.2 wt% NaCl eq. Fluid inclusions in the main and late-stage quartz and calcite are dominated by aqueous inclusions as well as hydrocarbon- and CO₂-rich inclusions. The presence of abundant hydrocarbon fluid inclusions in the gold deposits provides evidence that at least during main periods of the hydrothermal activity responsible for gold mineralization, the ore fluids consisted of an aqueous solution and an immiscible hydrocarbon phase. Aqueous inclusions in the main stage quartz associated with gold mineralization (stage II) typically have a homogenization temperature range of 200–230°C and a modal salinity around 5.3 wt% NaCl eq. Homogenization temperatures and salinities of aqueous inclusions in the late-stage drusy quartz and calcite (stage III) typically range from 120°C to 160°C and from 2.0 to 5.6 wt% NaCl eq., respectively. In the paleo-oil reservoirs, aqueous fluid inclusions with an average homogenization temperature of 80°C are dominant in early diagenetic calcite. Fluid inclusions in late diagenetic pore- and fissure-filling calcite associated with bitumen are dominated by liquid C₂H₆, vapor CH₄, CH₄–H₂O, and aqueous inclusions, with a typical homogenization temperature range of 90°C to 180°C and a salinity range of 2–8 wt% NaCl eq. It is suggested that the hydrocarbons may have been trapped at relatively low temperatures, while the formation of gold deposits could have occurred under a wider and higher range of temperatures. The timing of gold mineralization in the Youjiang basin is still in dispute and a wide range of ages has been reported for individual deposits. Among the limited isotopic data, the Rb–Sr date of 206 ± 12 Ma for Au-bearing hydrothermal sericite at Jinya as well as the Re–Os date of 193 ± 13 Ma on auriferous arsenian pyrite and ⁴⁰Ar/³⁹Ar date of 194.6 ± 2 Ma on vein-filling sericite at Lannigou may provide the most reliable age constraints on gold mineralization. This age range is comparable with the estimated petroleum charging age range of 238–185 Ma and the Sm–Nd date of 182 ± 21 Ma for the pore- and fissure-filling calcite associated with bitumen at the Shitouzhai paleo-oil reservoir, corresponding to the late Indosinian to early Yanshanian orogenies in South China. The close association of Carlin-type gold deposits and paleo-oil reservoirs, the paragenetic coexistence of bitumens with ore-stage minerals, the presence of abundant hydrocarbons in the ore fluids, and the temporal coincidence of gold mineralization and hydrocarbon accumulation all support a coeval model in which the gold originated, migrated, and precipitated along with the hydrocarbons in an immiscible, gold- and hydrocarbon-bearing, basinal fluid system.     

Geology and geochemistry of telluride-bearing Au deposits in the Pingyi area, Western Shandong, China

Summary Telluride-bearing gold deposits of the Pingyi area, western Shandong, China, are located on the southeastern margin of the North China Craton. There are two main types of deposits: (i) mineralized cryptoexplosive breccia, e.g., Guilaizhuang; and (ii) stratified, finely-disseminated mineralization hosted in carbonate rocks, e.g., Lifanggou and Mofanggou deposits. In Guilaizhuang, the cryptoexplosive breccia is formed within rocks of the Tongshi complex and Ordovician dolomite. The mineralization is controlled by an E–W-trending listric fault. Stratified orebodies of the Lifanggou and Mofanggou deposits are placed along a NE-trending, secondary detachment zone. They are hosted within dolomitic limestone, micrite and dolomite of the Early-Middle Cambrian Changqing Group. The mineralization in the ore districts is considered to be related to the Early Jurassic Tongshi magmatic complex that formed in a continental arc setting on the margin of the North China Craton. The host rocks are porphyritic and consist predominantly of medium- to fine-grained diorite and pyroxene (hornblende)-bearing monzonite. SHRIMP U–Pb zircon dating of diorites give a ²⁰⁶Pb/²³⁸U weighted mean age of 175.7 ± 3.8 Ma. This is interpreted as representing the crystallization age of the Tongshi magmatic complex. Considering the contact relationships between the magmatic and host sedimentary rocks, as well as the genetic link with the deposits, we conclude that this age is relevant also for the formation of mineralization in the Pingyi area. We hence consider that the deposits formed in the Jurassic. The principal gold minerals are native gold, electrum and calaverite. Wall-rock alteration comprises pyritization, fluoritization, silicification, carbonatization and chloritization. Fluid inclusion studies indicate that all the analyzed inclusions are of two-phase vapor–liquid NaCl–H₂O type. Homogenization temperatures of the fluid inclusions vary from 103 °C to 250 °C, and the ice melting temperatures range from −2.5 °C to −13.5 °C, corresponding to a salinity range of 4.65 to 17.26 wt.% NaCl equiv. The δ³⁴S values of pyrite associated with gold mineralization exhibit a narrow range of −0.71 to + 2.99‰, implying that the sulfur was probably derived from the mantle and/or dioritic magma. The δ¹³C_PDB values of the fluid inclusions in calcite range from −7.3 to 0.0‰. The δ¹⁸O_SMOW values of vein quartz and calcite range from 11.5 to 21.5‰, corresponding to δ¹⁸O_fluid values of −1.1 to 10.9‰; δD values of the fluid inclusions vary between −70 and −48‰. The isotope data for all three deposits suggest mixing of ore-forming fluids derived from the mantle and/or magma with different types of fluids at shallow levels. Pressure release and boiling of the fluids, as well as fluid-rock interaction (Lifanggou and Mofanggou) and mixing of magmatically-derived fluids with meteoritic waters (Guilaizhuang) played an important role in the ore-forming processes.     

The Daduhe gold field at the eastern margin of the Tibetan Plateau: He, Ar, S, O, and H isotopic data and their metallogenic implications

The Daduhe gold field comprises several shear-zone-controlled Tertiary lode gold deposits distributed at the eastern margin of the Tibetan Plateau. The deposits are hosted in a Precambrian granite–greenstone terrane within the Yangtze Craton. The gold mineralization occurs mainly as auriferous quartz veins with minor sulphide minerals. Fluid inclusions in pyrite have ³He/⁴He ratios of 0.16 to 0.86 R_a, whereas their ⁴⁰Ar/³⁶Ar ratios range from 298 to 3288, indicating a mixing of fluids of mantle and crust origins. The δ³⁴S values of pyrite are of 0.7–4.2‰ (n = 12), suggesting a mantle source or leaching from the mafic country rocks. δ¹⁸O values calculated from hydrothermal quartz are between − 1.5‰ and + 6.0‰ and δD values of the fluids in the fluid inclusions in quartz are − 39‰ and − 108‰. These ranges demonstrate a mixing of magmatic/metamorphic and meteoric fluids. The noble gas isotopic data, along with the stable isotopic data suggest that the ore-forming fluids have a dominantly crustal source with a significant mantle component.     

Isotope geochemistry of ore fluids for the Dongsheng sandstone-type uranium deposit, China

The Dongsheng sandstone-type uranium deposit is one of the large-sized sandstone-type uranium deposits discovered in the northern part of the Ordos Basin of China in recent years. Geochemical characteristics of the Dongsheng uranium deposit are significantly different from those of the typical interlayered oxidized sandstone-type uranium ore deposits in the region of Middle Asia. Fluid inclusion studies of the uranium deposit showed that the uranium ore-forming temperatures are within the range of 150–160℃. Their 3He/4He ratios are within the range of 0.02–1.00 R/Ra, about 5–40 times those of the crust. Their 40Ar/36Ar ratios vary from 584 to 1243, much higher than the values of atmospheric argon. The δ18OH2O and δD values of fluid inclusions from the uranium deposit are -3.0‰– -8.75‰ and -55.8‰– -71.3‰, respectively, reflecting the characteristics of mixed fluid of meteoric water and magmatic water. The δ18OH2O and δD values of kaolinite layer at the bottom of the uranium ore deposit are 6.1‰ and -77‰, respectively, showing the characteristics of magmatic water. The δ13CV-PDB and δ18OH2O values of calcite veins in uranium ores are -8.0‰ and 5.76‰, respectively, showing the characteristics of mantle source. Geochemical characteristics of fluid inclusions indicated that the ore-formation fluid for the Dongsheng uranium deposit was a mixed fluid of meteoric water and deep-source fluid from the crust. It was proposed that the Jurassic-Cretaceous U-rich metamorphic rocks and granites widespread in the northern uplift area of the Ordos Basin had been weathered and denudated and the ore-forming elements, mainly uranium, were transported by meteoric waters to the Dongsheng region, where uranium ores were formed. Tectonothermal events and magmatic activities in the Ordos Basin during the Mesozoic made fluids in the deep interior and oil/gas at shallow levels upwarp along the fault zone and activated fractures, filling into U-bearing clastic sandstones, thus providing necessary energy for the formation of uranium ores.     

Cl/Br ratios and stable chlorine isotope analysis of magmatic–hydrothermal fluid inclusions from Butte,Montana and Bingham Canyon,Utah

A bulk geochemical study has been carried out on fluid inclusion leachates extracted from quartz veins from porphyry Cu deposits in Butte, Montana, USA and Bingham Canyon, Utah, USA. The leachates mostly represent low-salinity magmatic–hydrothermal fluid inclusions. Their halogen ratios (Br/Cl) of fluid inclusion leachates were determined by ion chromatography, and δ³⁷Cl values of the leachates were measured by continuous-flow isotope ratio mass spectrometry. Br/Cl ratios from early pre-Main stage and later Main stage veins at Butte range from 0.60 to 1.88 × 10⁻³ M. Ratios are similar in pre-Main stage veins with sericite bearing selvages and Main stage samples ranging from 0.81 to 1.08 × 10⁻³ and from 0.92 to 1.88 × 10⁻³ M, respectively, clustering below seawater (1.54 × 10⁻³ M) and overlapping mantle values (~1–2 × 10⁻³ M). Two samples associated with early pre-Main stage potassic alteration yield distinctly lower Br/Cl ratios of 0.60 and 0.64 × 10⁻³ M. Butte δ³⁷Cl values range from −0.8‰ to −2.3‰ with no significant difference between pre-Main stage and Main stage samples. Br/Cl ratios for quartz veins from Bingham Canyon range from 0.18 to 3.68 × 10⁻³ M. Br/Cl ratios from Bingham range above and below previously reported for porphyry copper deposits. In contrast to Butte, δ³⁷Cl values for Bingham are lower, ranging from −0.9‰ to −4.1‰. In the absence of any processes which can significantly fractionate chlorine isotopes at high temperatures, we suggest that the porphyry system at Bingham, and to a lesser extent at Butte, have inherited negative chlorine isotopic signatures from the subducting slab generated at low temperatures.     

Gold ore-forming fluids of the Tanami region, Northern Australia

Fluid inclusion studies have been carried out on major gold deposits and prospects in the Tanami region to determine the compositions of the associated fluids and the processes responsible for gold mineralization. Pre-ore, milky quartz veins contain only two-phase aqueous inclusions with salinities ≤19 wt% NaCl eq. and homogenization temperatures that range from 110 to 410°C. In contrast, the ore-bearing veins typically contain low to moderate salinity (<14 wt% NaCl eq.), H₂O + CO₂ ± CH₄ ± N₂-bearing fluids. The CO₂-bearing inclusions coexist with two-phase aqueous inclusions that exhibit a wider range of salinities (≤21 wt% NaCl eq.). Post-ore quartz and carbonate veins contain mainly two-phase aqueous inclusions, with a last generation of aqueous inclusions being very CaCl₂-rich. Salinities range from 7 to 33 wt% NaCl eq. and homogenization temperatures vary from 62 to 312°C. Gold deposits in the Tanami region are hosted by carbonaceous or iron-rich sedimentary rocks and/or mafic rocks. They formed over a range of depths at temperatures from 200 to 430°C. The Groundrush deposit formed at the greatest temperatures and depths (260–430°C and ≤11 km), whereas deposits in the Tanami goldfield formed at the lowest temperatures (≥200°C) and at the shallowest depths (1.5–5.6 km). There is also evidence in the Tanami goldfield for late-stage isothermal mixing with higher salinity (≤21 wt% NaCl eq.) fluids at temperatures between 100 and 200°C. Other deposits (e.g., The Granites, Callie, and Coyote) formed at intermediate depths and at temperatures ranging from 240 to 360°C. All ore fluids contained CO₂ ± N₂ ± CH₄, with the more deeply formed deposits being enriched in CH₄ and higher level deposits being enriched in CO₂. Fluids from deposits hosted mainly by sedimentary rocks generally contained appreciable quantities of N₂. The one exception is the Tanami goldfield, where the quartz veins were dominated by aqueous inclusions with rare CO₂-bearing inclusions. Calculated δ ¹⁸O values for the ore fluids range from 3.8 to 8.5‰ and the corresponding δD values range from −89 to −37‰. Measured δ ¹³C values from CO₂ extracted from fluid inclusions ranged from −5.1 to −8.4‰. These data indicate a magmatic or mixed magmatic/metamorphic source for the ore fluids in the Tanami region. Interpretation of the fluid inclusion, alteration, and structural data suggests that mineralization may have occurred via a number of processes. Gold occurs in veins associated with brittle fracturing and other dilational structures, but in the larger deposits, there is also an association with iron-rich rocks or carbonaceous sediments, suggesting that both structural and chemical controls are important. The major mineralization process appears to be boiling/effervescence of a gas-rich fluid, which leads to partitioning of H₂S into the vapor phase resulting in gold precipitation. However, some deposits also show evidence of desulfidation by fluid–rock interaction and/or reduction of the ore-fluid by fluid mixing. These latter processes are generally more prevalent in the higher crustal-level deposits.     

Origin of fluids in iron oxide–copper–gold deposits: constraints from δ 37Cl, 87Sr/86Sri and Cl/Br

The origin of the hypersaline fluids (magmatic or basinal brine?), associated with iron oxide (Cu–U–Au–REE) deposits, is controversial. We report the first chlorine and strontium isotope data combined with Cl/Br ratios of fluid inclusions from selected iron oxide–copper–gold (IOCG) deposits (Candelaria, Raúl–Condestable, Sossego), a deposit considered to represent a magmatic end member of the IOCG class of deposit (Gameleira), and a magnetite–apatite deposit (El Romeral) from South America. Our data indicate mixing of a high δ ³⁷Cl magmatic fluid with near 0‰ δ ³⁷Cl basinal brines in the Candelaria, Raúl–Condestable, and Sossego IOCG deposits and leaching of a few weight percent of evaporites by magmatic-hydrothermal (?) fluids at Gameleira and El Romeral. The Sr isotopic composition of the inclusion fluids of Candelaria, Raúl–Condestable, and El Romeral confirms the presence of a non-magmatic fluid component in these deposits. The heavy chlorine isotope signatures of fluids from the IOCG deposits (Candelaria, Raúl–Condestable, Sossego), reflecting the magmatic-hydrothermal component of these fluids, contrast with the near 0‰ δ ³⁷Cl values of porphyry copper fluids known from the literature. The heavy chlorine isotope compositions of fluids of the investigated IOCG deposits may indicate a prevailing mantle Cl component in contrast to porphyry copper fluids, an argument also supported by Os isotopes, or could result from differential Cl isotope fractionation processes (e.g. phase separation) in fluids of IOCG and porphyry Cu deposits.     

Ore-forming fluids associated with granite-hosted gold mineralization at the Sanshandao deposit, Jiaodong gold province, China

The Sanshandao gold deposit, with total resources of more than 60 t of gold, is located in the Jiaodong gold province, the most important gold province of China. The deposit is a typical highly fractured and altered, disseminated gold system, with high-grade, quartz-sulphide vein/veinlet stockworks that cut Mesozoic granodiorite. There are four stages of veins that developed in the following sequence: (1) quartz-K-feldspar-sericite; (2) quartz-pyrite±arsenopyrite; (3) quartz-base metal sulfide; and (4) quartz-carbonate. Fluid inclusions in quartz and calcite in vein/veinlet stockworks contain C-O-H fluids of three main types. The first type consists of dilute CO₂–H₂O fluids coeval with the early vein stage. Molar volumes of these CO₂–H₂O fluid inclusions, ranging from 50–60 cm³/mol, yield estimated minimum trapping pressures of 3 kbar. Homogenization temperatures, obtained mainly from CO₂–H₂O inclusions with lower CO₂ concentration, range from 267–375 °C. The second inclusion type, with a CO₂–H₂O±CH₄ composition, was trapped during the main mineralizing stages. These fluids may reflect the CO₂–H₂O fluids that were modified by fluid/rock reactions with altered wallrocks. Isochores for CO₂-H₂O±CH₄ inclusions, with homogenization temperatures ranging from 204–325 °C and molar volumes from 55 to 70 cm³/mol, provide an estimated minimum trapping pressure of 1.2 kbar. The third inclusion type, aqueous inclusions, trapped in cross-cutting microfractures in quartz and randomly in calcite, are post-mineralization, and have homogenization temperatures between 143–228 °C and salinities from 0.71–7.86 wt% NaCl equiv. Stable isotope data show that the metamorphic fluid contribution is minimal and that ore fluids are of magmatic origin, most likely sourced from 120–126 Ma mafic to intermediate dikes. This is consistent with the carbonic nature of the fluid, and the cross-cutting nature of those deposits relative to the host Mesozoic granitoid.Editorial handling: R.J. Goldfarb     

Atacamite formation by deep saline waters in copper deposits from the Atacama Desert,Chile: evidence from fluid inclusions,groundwater geochemistry,TEM, and <Superscript>36</Superscript>Cl data

The presence of large amounts of atacamite in oxide zones from ore deposits in the Atacama Desert of northern Chile requires saline solutions for its formation and hyperarid climate conditions for its preservation. We investigated the nature and origin of atacamite-forming solutions by means of coupling groundwater geochemical analyses with fluid inclusion data, high-resolution mineralogical observations, and chlorine-36 (³⁶Cl) data in atacamite from the Mantos Blancos and Spence Cu deposits. In both deposits, the salinities of fluid inclusions in atacamite are comparable to those measured in saline groundwaters sampled from drill holes. The average salinity of fluid inclusions in atacamite for the Mantos Blancos and Spence deposits (~7–9 and 2–3 wt.% NaCl_eq, respectively) are strongly correlated to the salinities at which gypsum supersaturates from groundwaters in both deposits (total dissolved solids ~5–9 and 1–3 wt.% NaCl_eq, respectively). This correlation is confirmed by transmission electron microscopy observations of atacamite-bearing samples, revealing an intimate association between atacamite and gypsum that can be traced down to the nanometer scale. ³⁶Cl data in atacamite provide new lines of evidence concerning the origin and age of the saline waters that formed atacamite in various stratabound and porphyry Cu deposits from the Atacama Desert. All atacamite samples show very low ³⁶Cl-to-Cl ratios (11 × 10⁻¹⁵ to 28 × 10⁻¹⁵ at at⁻¹), comparable to previously reported ³⁶Cl-to-Cl ratios of deep formation waters and old groundwaters. In addition, ³⁶Cl-to-Cl ratios in atacamite correlate with U and Th concentration in the host rocks but are independent from distance to the ocean. This trend supports an interpretation of the low ³⁶Cl-to-Cl ratios in atacamite as representing subsurface production of fissiogenic ³⁶Cl in secular equilibrium with the solutions involved in atacamite formation. Therefore, ³⁶Cl in atacamite strongly suggest that the chlorine in saline waters related to atacamite formation is old (>1.5 Ma) but that atacamite formation occurred more recently (<1.5 Ma) than suggested in previous interpretations. Our data provide new constraints on the origin of atacamite in Cu deposits from the Atacama Desert and support the recent notion that the formation of atacamite in hyperarid climates such as the Atacama Desert is an ongoing process that has occurred intermittently since the onset of hyperaridity.