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The Morelos district, located in the center of the Guerrero gold belt, Guerrero State, southern Mexico, has been the site of several recent gold ± copper skarn discoveries (total of ~8.5 Moz Au) associated with Upper Cretaceous-Paleocene granodiorite intrusions. The Limon, Guajes, and Media Luna skarn deposits developed along the contact of the El Limon granodiorite and the sedimentary host rocks. Native gold is associated with retrograde alteration of garnet-pyroxene skarn and is accompanied by native bismuth as well as telluride and sulfide minerals. The Media Luna deposit is characterized by a distinct magnesium-rich skarn mineralogy and contains an average of ~1 wt % Cu, in addition to gold and silver. This distinguishes it from the other gold-only skarn deposits in the Guerrero gold belt. This observation suggests that skarns in the Guerrero gold belt, which replaced magnesium-rich sedimentary protoliths, may host significant copper resources in addition to gold. Uranium-lead laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) zircon ages of the El Limon granodiorite range from 66.86 ± 0.40 to 65.88 ± 0.79 Ma. Preskarn molybdenite-quartz veins cut through the El Limon granodiorite and yield Re-Os molybdenite ages between 66.63 ± 0.22 and 65.55 ± 0.25 Ma. A series of pre-, syn-, and postskarn porphyritic dikes intruded the El Limon granodiorite, having zircon ages ranging from 65.9 ± 1.1 to 64.68 ± 0.38 Ma. The timing of skarn formation at Limon and Media Luna was constrained to 64.6 ± 1.2 to 63.2 ± 1.0 Ma, applying U-Pb LA-ICP-MS to garnet. The ubiquitous presence of garnet in skarn deposits and the time- and cost-efficiency of in situ geochronology are striking advantages of this method to constrain the timing of mineralization.

The Montecristo district, northern Chile, is one of the few places worldwide where there is a direct relationship between magnetite-(apatite) (MtAp) mineralization and iron oxide-copper–gold (IOCG) mineralization. The MtAp mineralization includes Ti-poor magnetite, fluorapatite, and actinolite and is crosscut and partially replaced by a younger IOCG mineralization that includes a second generation of actinolite and magnetite with quartz, chalcopyrite, pyrite, and molybdenite. The MtAp stage at Montecristo is interpreted as the crystallized iron-rich melts that used the pre-existing structures of the Atacama Fault System as conduits. These rocks later acted as a trap for hydrothermal IOCG mineralization. Geochronology data at Montecristo indicate that the host diorite (U–Pb zircon 153.3 ± 1.8 Ma, 2-sigma), MtAp mineralization (40Ar-39Ar in actinolite, 154 ± 2 Ma and 153 ± 4 Ma, 2-sigma), and the IOCG event (Re-Os on molybdenite, 151.8 ± 0.6 Ma, 2-sigma) are coeval within error and took place in a time span of less than 3.4 Ma. The εHfi and εNdi values of the host diorite are + 8.0 to + 9.8 and + 4.3 to + 5.4, respectively. The whole-rock 87Sr/86Sri values of the IOCG mineralization (0.70425 to 0.70442) are in the lower end of those of the MtAp mineralization (0.70426–0.70629). In contrast, εNdi values for the IOCG mineralization (+ 5.4 and + 5.7) fall between those of the MtAp rocks (+ 6.6 to + 7.2) and the host diorite, which suggests that the IOCG event was related to fluids having a more crustal Nd (εNdi < + 5.7) composition than the MtAp mineralization. This likely reflects the mixing of Nd from the MtAp protolith and a deep magmatic-hydrothermal source, very likely an unexposed intrusion equivalent to the host diorite. Sulfur isotope compositions (δ34S, + 0.3 to + 3.4‰) are consistent with a magmatic source., NSERC discovery grant to J.M. Hanchar (RGPIN/004649-2015), RTI2018-099157-A-I00 (MCI/AEI/FEDER, UE) research grant to F. Tornos.

The ages of sedimentation and copper-silver mineralization in the late Meso- to Neoproterozoic Kalahari Copperbelt in Botswana, an economically significant copper province, have previously been poorly constrained within an ~600 m.y. period that spans the Neoproterozoic from the assembly and breakup of Rodinia to the assembly of Gondwana. Rhenium-osmium geochronology of molybdenite and copper sulfide minerals and U-Th-Pb laser ablation split-stream inductively coupled plasma-mass spectrometry (LASS ICP-MS) analysis of xenotime grains are utilized to provide absolute and relative age data on the host rocks and mineralizing events within the Ghanzi Ridge region of the Kalahari Copperbelt. The data reveal a prolonged history of events, which is partially comparable with depositional and mineralizing events in the neighboring Central African Copperbelt. Abundant disseminated molybdenite is located within a shale layer near the base of the Proterozoic D’Kar Formation at the Northeast Mango Two deposit. Unusual molybdenite textures suggest organic matter may have been a precursor. Two molybdenite separates from a small calcite-molybdenite stringer in a wall-rock fragment that is enclosed within an epigenetic quartz-calcite-chalcopyrite vein with ill-defined and mismatched margins yielded Re-Os ages of 981 ± 3 and 981 ± 7 Ma. These ages indicate an early hydrothermal mineralizing event in the basin. A xenotime inclusion intergrown with molybdenite and chalcopyrite within the epigenetic vein yielded a younger U-Th-Pb age of 538 ± 8 Ma, suggesting two mineralizing events are preserved in a complex 6-cm-wide vein. Based on vein texture and alteration, the ages represent an ~981 Ma calcite-molybdenite mineralization event overprinted by an ~538 Ma quartz-chalcopyrite-molybdenite mineralization event, perhaps during reopening of the vein. Re-Os and U-Th-Pb geochronology were utilized at the Zone 6 deposit on minerals associated with a hydrothermal quartz-calcite-chalcocite-idaite-bornite vein. Several authigenic xenotime grains that occur along the margin of the vein yielded three concordant U-Th-Pb ages that indicate xenotime growth at ~950 to 925 Ma while other xenotime grains in a similar position yielded mostly discordant data, suggesting disturbance of the isotopic system in the xenotime grains. A coprecipitated chalcocite-idaite mixture within the hydrothermal vein produced an Re-Os age of 549.0 ± 11.2 Ma. Re-Os analysis obtained from a coprecipitated molybdenite-bornite mixture at the Northeast Fold deposit yielded an age of 515.9 ± 2 Ma. Together, the earliest Neoproterozoic Re-Os molybdenite and U-Th-Pb xenotime ages provide both a minimum depositional age constraint for the lowermost D’Kar Formation and clear evidence that diagenetic hydrothermal mineralizing events took place within the Ghanzi basin. The timing of this mineralizing event corresponds with a poorly documented regional thermal event that affected the northern margin of the Kalahari craton during the final stages of the assembly of Rodinia at ~980 Ma. The lower to middle Ghanzi Group of the Kalahari Copperbelt is at least 100 m.y. older than the host rocks within the neighboring Central African Copperbelt, which are associated with the breakup of Rodinia. The latest Neoproterozoic to Cambrian Re-Os and U-Th-Pb ages indicate that hydrothermal copper-silver mineralizing events occurred during the Pan-African (~600–480 Ma) fold-thrust evolution of the Ghanzi-Chobe zone and were broadly synchronous with widespread epigenetic hydrothermal copper-cobalt mineralizing events in the adjacent Central African Copperbelt.

The Ok Tedi copper-gold mine in Western Province, Papua New Guinea, is situated in the western part of the Ok Tedi Complex where monzodiorite to quartz monzonite intrusions are associated with porphyry- and skarn-style copper-gold mineralization. The Pleistocene age of the intrusive rocks and mineralization provides an opportunity to study the longevity of the magmatic and hydrothermal evolution at Ok Tedi through U-Pb dating of zircon and high-precision Re-Os dating of molybdenite. Six main phases of intrusive rocks can be recognized within the mine area, with the sequence of intrusion indicated by contact relationships. Each has been dated by the SHRIMP U-Pb technique with correction for Th-U disequilibrium based on the U and Th content of each sample. In order of intrusion from oldest to youngest these include: Sydney Monzodiorite (1.368 ± 0.045 Ma), Warsaw Monzodiorite (1.269 ± 0.039 Ma), Kalgoorlie Monzodiorite (1.261 ± 0.050 Ma), Ningi Quartz Monzonite Porphyry (QMP)(1.229 ± 0.051 Ma), Bonn Quartz Monzonite (1.219 ± 0.040 Ma), and Fubilan QMP (1.213 ± 0.049 Ma). The intrusions are alkaline, high K to shoshonitic rocks with high Sr/Y ratios typical of Cu-fertile arc magmas. Chondrite-normalized REE patterns have minor or no negative Eu anomalies and downward sloping to listric-shaped HREE patterns typical of arc magmas in which high water contents supress plagioclase fractionation in favor of an evolution by hornblende ± garnet ± titanite fractionation. Cu-Au mineralization at Ok Tedi can be divided into four main stages based on crosscutting relationships: (1) skarn-endoskarn and associated vein-style mineralization in the Darai Limestone, Ieru siltstone, and Sydney Monzodiorite; (2) porphyry-style veins and breccias within the Ningi QMP and older intrusions, and at Siltstone Ridge: (3) porphyry-style veins and breccias in the Fubilan QMP and older intrusions: and (4) skarn-style mineralization in the lower part of the Darai Limestone along the Taranaki thrust. High-precision Re-Os dating of molybdenite has enabled a chronology to be established for the first three stages. Molybdenite from a quartz-mushketovite-epidote-carbonate-pyrite-chalcopyrite-molybdenite vein in clinopyroxene- and garnet-altered Sydney Monzodiorite has an age of 1.3206 ± 0.0020 Ma, and this dates the formation of the Gold Coast and Berlin skarns. Molybdenite from a quartz-pyrite-chalcopyrite-molybdenite vein in the sericite-altered Sydney Monzodiorite yields an age of 1.3166 ± 0.0043 Ma, and a quartz-pyrite-chalcopyrite-molybdenite vein with K-feldspar alteration selvages hosted in Ieru siltstone beneath the Gold Coast skarn has an age of 1.3031 ± 0.0015 Ma. Samples of molybdenite from quartz-sulfide veins from Siltstone Ridge have ages of 1.2116 ± 0.0029 and 1.2078 ± 0.0031 Ma. Molybdenite from a quartz-K-feldspar-pyrite-molybdenite vein, which overprints propylitic alteration in the Sydney Monzodiorite, has an age of 1.2120 ± 0.0024 Ma. These samples date porphyry-style mineralization in and around the Ningi QMP and at Siltstone Ridge. A sample of molybdenite from the matrix of hydrothermal intrusive breccia in the Fubilan QMP has an age of 1.2146 ± 0.0020 Ma, similar to the age of the adjacent Siltstone Ridge mineralization, and is interpreted to have been mechanically incorporated into the breccia during its formation. Several samples have been dated from the Fubilan porphyry system, including molybdenite from the matrix of a hydrothermal intrusive breccia (1.1648 ± 0.0020 Ma) and three samples from veins which postdate the breccias: a vuggy quartz-sulfide vein (1.1532 ± 0.0027 Ma), chalcopyrite-pyrite-molybdenite vein (1.1446 ± 0.0028 Ma), and duplicate analyses of a molybdenite-only vein (1.1326 ± 0.0034 and 1.1297 ± 0.0026 Ma) in agreement at 2σ. Molybdenite from a quartz-K-feldspar-biotite-magnetite-pyrite-chalcopyrite-molybdenite vein in endoskarn-altered Sydney Monzodiorite (beneath the Gold Coast skarn) has an age of 1.1459 ± 0.0012 Ma, and a similar vein without magnetite hosted in Warsaw Monzodiorite has an age of 1.1438 ± 0.0042 Ma, both within error of the chalcopyrite-pyrite-molybdenite vein in Fubilan QMP. Intrusive rocks in the Ok Tedi mine were emplaced over a period of approximately 200,000 years, with Cu-Au mineralization formed in discrete episodes of much shorter duration. The Gold Coast skarn and associated porphyry-style veins in Sydney Monzodiorite and Ieru siltstone formed in 14,000 to 21,000 years (n = 3), the Siltstone Ridge porphyry system in 2,000 to 12,000 years (n = 4), and the Fubilan porphyry system in 31,000 to 40,000 years (n = 6). The Taranaki skarn has not been dated in the mine area due to a lack of molybdenite, but geologic relationships indicate it is younger than the Fubilan QMP.

The Re-Os geochronometer constrains the timing of petroleum formation and provides an oil-source isotopic correlation tool for improved geologic knowledge and exploration success. However, the effects of secondary processes that may sometimes complicate interpretations are not well understood. This paper discusses Re-Os systematics in a petroleum system that experienced extensive asphaltene precipitation upon mixing of different oil phases. The Solveig oil field (formerly Luno II), Utsira high, Norwegian North Sea, comprises three structural compartments that capture different stages of the mixing process. In the central compartment, an Re-Os age of circa 40 Ma for whole-rock extracts sampling the residual (asphaltene-rich and biodegraded) oil below the oil–water contact is consistent with burial models for Paleocene–Miocene generation. A 10-m-thick, asphaltene-rich (65 wt. %) tar mat zone precipitated upon mixing of at least two components does not yield meaningful ages. The Re-Os isochrons for the free-flowing crude oil and whole-rock extracts from the oil leg above the tar mat zone indicate circa 10 to 0 Ma ages for the younger oil phase, supporting independent estimates for recent oil influx. Decreasing 187Os/188Os from maltenes to asphaltenes in oil from the southeastern compartment are highly unusual and provide geochemical evidence for recent mixing, consistent with the strong asphaltene-in-oil gradient. Very low and remarkably uniform Re/Os ratios for all petroleum phases, combined with relatively low and uniform 187Os/188Os ratios, strongly support isotopic overprint of the Re-Os system, likely during water–oil interaction. Despite this overprint, Re-Os ages retain information on primary events, whereas initial 187Os/188Os ratios are strongly affected.

Petroleum systems are inherently complex, comprising multiple components and processes, which variably interact in space and time to form petroleum accumulations. Improved understanding of these complex systems requires a holistic approach of integrating diverse geological, geophysical and organic and inorganic geochemical data. Here, we present an applied and comprehensive Re-Os geochronological and geochemical study on the Brynhild petroleum system from the Norwegian North Sea. Essential components of this system include shale source rocks of the Mandal and Farsund Formations, reservoir sandstones of the Ula Formation and their bitumen extracts, and produced Brynhild crude oil. Rock-Eval, trace metal and Re-Os data reveal the excellent oil-generation potential of the shaley source rocks (high contents of organic matter containing large amounts of type I kerogens) and constrain their depositional conditions (anoxic bottom waters in a high-productivity regime driven by enhanced supply of land-derived nutrients). Seven Re-Os shale ages between ~146 and ~134 Ma are consistent with existing Volgian–Ryazanian age estimates and constrain the initial 187Os/188Os of the shales to ~0.52 in the lowermost Farsund Formation and ~0.75 in the uppermost Mandal Formation. Solvent-extracted reservoir rocks of the Ula Formation contain insoluble organic matter with type III–type IV kerogens likely supplied by erosion of older (a precise 179 Ma Re-Os age with unrealistically low initial 187Os/188Os) coal-bearing sediments or organic-rich shales. The Brynhild crude oil has relatively low 187Os/188Os and a generation age of ~44 Ma based on an asphaltene-only Re-Os isochron. Maltenes from the Brynhild crude oil are isotopically affected by interaction with organic-rich source rocks that represent the seal for the Brynhild oil field. Compared with the crude oil, bitumen from Ula Formation sandstones have contrasting Re-Os properties: high 187Os/188Os ratios and young generation ages between 8 and 0 Ma based on asphaltene-bitumen-maltene Re-Os triplets, asphaltene-only Re-Os regressions, and Re Os model ages for components with extremely high 187Re/188Os. The 44 Ma and 8–0 Ma Re-Os ages agree well with regional burial models that indicate oil generation from ~44 Ma to present day. A genetic link between crude oil and bitumen is indicated by their similar alkane patterns, V and Ni contents, and V/Ni and pristane/phytane ratios. Modeling of 187Os/188Os for individual organic components through time shows that shales of the Mandal Formation developed 187Os/188Os ratios that match those of the crude oil and bitumen at ~44 Ma and ~8 Ma, respectively, and therefore confirm the source for both hydrocarbon phases. We suggest that bitumen formed during in-reservoir mixing of a ~44 Ma old early mature, asphaltene-poor oil (Brynhild crude oil) with an ~8 Ma old asphaltene-rich oil.

Strandings of various types of bitumen along the coast of southern Australia are long known. Among these, brittle, angular lumps termed ‘asphaltites’ are possibly sourced from Cretaceous source rocks linked to an oceanic anoxic event (OAE), but the exact source remains unclear. The unusual chemical composition of these asphaltites and their survival during transport and shoreline stranding suggest that they formed by nearby submarine seepage of asphaltene-rich crude oils. Here, we provide a detailed organic and inorganic geochemical characterization of asphaltites to constrain their origin and age. High-pressure hydropyrolysis (HyPy) of asphaltene fractions from ten asphaltites released similar assemblages of macromolecularly bound compounds, suggesting a common source for all asphaltites. Comprehensive gas chromatography–time-of-flight mass spectrometry (GC×GC-TOFMS) was used to compare these asphaltene-derived compounds with the maltene fractions, while compound specific isotope analysis (CSIA) was used to compare δ13C and δ2H of n-alkanes and isoprenoids. A large offset between the δ2H of the n-alkanes and isoprenoids suggests oil generation and expulsion at low thermal maturity. The mean concentrations of isorenieratane and chlorobactane, carotenoid derivatives indicative of photic zone euxinia (PZE), in the asphaltites were 8.8 ± 0.8 SEM µg g−1 and 1.4 ± 0.1 SEM µg g−1, respectively. A mean Aryl Isoprenoid Ratio of 0.75 (SD = 0.17) is accompanied by Pr/Ph of ∼1.2. These features strongly support persistent PZE conditions at the level expected for an OAE. Trace metal contents of the asphaltites, including low selenium and high vanadium concentrations, also support anoxic conditions. Rhenium-osmium (Re-Os) analyses constrain the age of asphaltite generation to 103 ± 22 Ma, with a relatively low initial 187Os/188Os ratio of 0.44 ± 0.18. Integrating local geologic knowledge with organic and inorganic geochemistry and Re-Os isotopic results, we identify a Cretaceous unit associated with OAE1a (∼125 Ma) as the most likely source of the asphaltites. Alternative scenarios involving source rocks deposited during OAE1b (∼112 Ma) are possible, but require rapid burial of organic-rich sediments to reach required maturation levels in a shorter time.

The calc-alkalic Mitchell Au-Cu-Ag-Mo porphyry deposit, hosted in intrusive rocks of the Stikine volcanic arc terrane of northwestern British Columbia, is the largest undeveloped gold resource in Canada, with 40.72 Moz of contained gold. It lies within the KSM trend, a 12-km-long linear porphyry array in the Sulphurets district. It is genetically related to Early Jurassic Sulphurets stocks: phase 1 diorite to monzodiorite hosts Cu-Au mineralization in potassic assemblages (stage 1), a phase 2 granodiorite plug cores a molybdenum halo (190.3 ± 0.8 Ma, 191.3 ± 0.7 Ma; Re-Os, molybdenite) that is accompanied by phyllic alteration (stage 2), and a poorly mineralized phase 3 diorite plug temporally overlaps with quartz-pyrophyllite alteration at shallow levels (stage 3). Two deformation events (D1 and D2), attributed to orogen-scale mid-Cretaceous transpression, structurally modified Mitchell. D1 deformation, expressed as steep E-striking pressure solution cleavage (S1) and related W-plunging folded veins (F1), is heterogeneously developed as a function of alteration type. D2 is divided into two progressive events: D2a, defined by N-plunging, folded veins (F2a), and D2b, defined by E-vergent thrust faults, including the Mitchell thrust fault, which offsets the updip continuation of Mitchell (the Snowfield deposit, 192.0 ± 1.0 Ma, 191.1 ± 0.8 Ma; Re-Os, molybdenite) ~1,600 m to the east-southeast. Host structures for the KSM trend may have been long-lived, N-striking basement lineaments that provided transcrustal magma and fluid pathways. East-trending intrusions, hydrothermal veins, alteration and metal distribution at Mitchell are attributed to subsidiary E-striking cross faults. These original anisotropies in turn influenced the geometry of Cretaceous faults and flattening domains within the deposit.

The Re-Os geochronometer can be applied to date petroleum, which is the end product of complex natural processes. Improved interpretation of natural Re-Os datasets requires identification of key controlling factors for Re-Os systematics and their isotopic imprint in oils. Here, we focus on the role of water in (re)setting the Re-Os geochronometer in oils, as formation waters and oils often coexist in basinal systems. To quantify Re-Os systematics during water-oil interaction, we performed a series of equilibration experiments between different oils and dilute aqueous solutions doped with Re and Os. The investigated parameters include the oil composition, water to oil ratio, interaction time and the initial Re-Os content in the aqueous solution. In experiments performed across a high concentration gradient, the oils fully homogenized with respect to their Os isotopic composition but had variable 187Re/188Os ratios. This indicates that the Re-Os geochronometer has been reset during water-oil interaction. However, in experiments investigating partial isotopic overprint, the crude oil and its maltene and asphaltene fractions preserved their isochron-derived age. Thus, the Re-Os radiometric clock of a single crude oil sample remains intact, even during partial equilibration of the 187Os/188Os ratio. These experimental findings provide a new foundation for interpretation of Re-Os systematics in natural water-hydrocarbon systems.

The Lar porphyry Cu-Mo deposit is located 20 km northeast of Zahedan in the Sistan Suture Zone (SSZ), in the southeastern part of Iran. Lar is a sub-economic porphyry Cu-Mo deposit with average grades of 0.16% Cu, 0.01% Mo, and 0.66 ppb Au. The Cu-Mo mineralization developed in post-collisional shoshonitic syenitic to monzonitic intrusions in an Oligocene igneous complex known as the Lar Igneous Complex (LIC). The host and country rocks have undergone variable degrees of supergene and hypogene alteration including silicic, potassic, propylitic, phyllic, and argillic alteration. The Cu-Mo mineralization is mainly controlled by NNW striking faults and fractures, and occurs as quartz veins and veinlets, disseminated sulfides, and stockworks. The mineralization can be divided into two types: hypogene and supergene. Hypogene mineralization is characterized by chalcopyrite, pyrite, bornite, molybdenite and magnetite, whereas supergene mineralization is characterized by enargite, covellite, chalcocite, digenite, malachite, azurite, and iron hydroxides. Sulfur isotope values for hypogene sulfides range from 0.28 to −1.76‰ and suggest an igneous source/or mantle-derived origin for sulfur. The δ18O values for quartz in mineralized quartz veins range from 9.6 to 11.5‰. These values would be in equilibrium with waters having calculated δ18OH2O values of 9.3–11.2‰, suggesting magmatic water. Re-Os dating of two molybdenite samples from two different drill holes yields dates of 29.72 ± 0.11 and 31.95 ± 0.11, suggesting that the system was active for at least 2.0 m.y.

In the Qarachilar Cu-Mo-Au deposit of the Ahar-Arasbaran metallogenic zone (AAMZ), northwest Iran, mineralization occurs as three quartz-sulfide veins that cut granodiorite-quartz monzodiorite rocks of the Qaradagh batholith (QDB). Ore formation can be divided into three stages, with chalcopyrite, molybdenite, and gold bearing pyrite appearing mainly in the first two stages. The main wall-rock alteration is silicification, and intermediate argillic, carbonate, and propylitic alteration. Fluid inclusion microthermometry indicates trapping of medium- to high-salinity (9.2-55 wt% NaCl equiv.) fluids at Qarachilar. Fluid inclusion trapping conditions are estimated to be 190 degrees C-530 degrees C and 0.1-3 kbar. The variable phase ratios as well as spatial coexisting of liquid and vapor-rich two-phase and halite-bearing multiphase fluid inclusions homogenizing over the same temperatures are consistent with fluid boiling during ore formation. Obtained delta O-18(H2O) values of quartz from ore stage veins are +5.7 parts per thousand to +9.7 parts per thousand, signifying that the ore-fluid system was predominantly magmatic water. The average calculated delta S-34(H2S) values are 1 +/- 1 parts per thousand for pyrite, chalcopyrite and molybdenite, consistent with a magmatic source for sulfur. Combined, the fluid inclusion and stable isotope data indicate that the ore-forming fluids at Qarachilar were magmatic in origin and were subsequently cooled and diluted by meteoric water. Fluid boiling and mixing facilitated hydrothermal alteration and mineralization. Molybdenite Re-Os dating shows that mineralization occurred at 42.35 +/- 0.16 Ma, coincident with formation of porphyry Cu-Mo mineralization at Agarak deposit, and Hanqasar, Aygedzor and Dastakert prospects in the Lesser Caucasus. However, Qarachilar is older than all porphyry Cu-Mo mineralization in the AAMZ and Urumieh-Dokhtar magmatic arc (UDMA), which suggests that collision between Arabia and Eurasia were oblique and thus diachronous. Our data suggest that mineralization at Qarachilar is related to collisional Eocene magmatic-hydrothermal activity related to Neo-Tethys subduction, and shares a number of similarities with the vein-type Cu-Mo-Au mineralization related to Cu-Mo porphyries.

The Central Lapland Greenstone Belt (CLGB) is well endowed with orogenic gold deposits along major shear zones and structural lineaments. In the northern part of the belt, the Kiistala Shear Zone (KiSZ) hosts the Suurikuusikko gold deposit (Kittila Mine), currently the largest gold producer in Europe. The Iso-Kuotko deposit is located 10 km to the north of Suurikuusikko along the same shear zone. Gold mineralization at Iso-Kuotko formed in two major stages: an early stage refractory gold mineralization with auriferous arsenopyrite with similarities to the ore at Suurikuusikko and a late, main stage mineralization with free gold in carbonate-quartz veins with abundant pyrrhotite, native bismuth and other sulphide minerals. This latter ore is absent at Suurikuusikko. Based on U-Pb dating, as well as Re-Os and Pb-isotope systematics of rock-forming and hydrothermal minerals, we evaluate the relationships between tectonic evolution and formation of gold deposits throughout the late Palaeoproterozoic in the northern part of the CLGB. Results from in situ U-Pb dating of zircon and petrographically well constrained hydrothermal monazite and xenotime by LA-ICPMS, and model age calculations using Re-Os isotopic data for arsenopyrite and in situ Pb-isotope data for galena from the Iso-Kuotko deposit provide evidence for multiple episodes of hydrothermal activity along the KiSZ. Data suggest coincident felsic magmatism and structurally controlled fluid flow events during wrench fault-dominated N-S shearing associated with early, micro-continent accretion ushering in the Svecofennian orogeny. This includes the formation of refractory gold ores at Suurikuusikko (1916 ± 19 Ma) and Iso-Kuotko (>1868 ± 15 Ma). Subordinate barren veining took place at ∼1830 Ma during transient extension between the accretion and final collision stage. Xenotime in late stage veins with visible gold at Iso-Kuotko yield U-Pb ages between 1761 ± 9 and 1770 ± 7 Ma. This time-interval is concurrent with widespread granitoid emplacement at the close of the Svecofennian orogeny. Disturbance of the Re-Os system in the early auriferous arsenopyrite can be connected to the late stage mineralizing processes. Pb isotope data suggest a mixed mantle and lower crust origin for fluids in the post-orogenic hydrothermal system. In situ U-Pb dating in polished thin sections in tandem with electron microprobe analyses of mineral compositions and detailed textural observations, highlights the utility of xenotime and monazite as robust geochronometers capable of recording repeated hydrothermal events in Paleoproterozoic orogenic systems. Results provide precise temporal constraints for orogenic gold mineralization and vital information to refine the tectonic evolution of the Central Lapland Greenstone Belt.

Precise and accurate measurements of the isotopic composition of rhenium (Re) in geologic samples are of paramount importance for the successful application of the Re-Os geochronometer. Two methods for chemical isolation of Re are used in the geochronology community – column chemistry using anion exchange resin and solvent-solvent extraction using a sodium hydroxide-acetone mixture. Despite their ubiquitous application, a systematic comparison of these two methods is missing. Here we compare Re-isotopic data on a variety of samples (sulfides, hydrocarbons, shales, and in-house standard solutions) that were processed by both chemical methods. Measured 185Re/187Re ratios for both methods have similar precision and overlap within the propagated long-term analytical reproducibility of ~1‰ for samples that yield moderate to strong intensities (>50 mV on the weaker Re mass). In contrast, measured 185Re/187Re ratios for most samples that yield less intense Re signals (

The final publication is available at Elsevier via https://doi.org/10.1016/j.gca.2017.06.046 © 2017. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/

The Chah-Firouzeh deposit with about 100 Mt ore reserves @ 0.5% Cu is a porphyry copper deposit located 14 km west of the Meiduk deposit in the northern section of the Kerman Cenozoic Magmatic Assemblage (KCMA), southeastern Iran. The mineralization is associated with a porphyry quartz-monzodiorite to quartz-diorite stock, which intruded into Eocene volcanic rocks consisting of andesite, basalt, and andesitic to dacitic tuff. Hydrothermal alteration types in the area include potassic, phyllic, and propylitic varieties. Silicic alteration locally occurred at the surface, while supergene argillic alteration overprinted the other alterations at shallow levels. Mineralization occurs as quartz-sulfide veinlets and stockworks, as well as disseminations in the porphyry body and volcanic host rocks, in association with potassic and phyllic alteration. Hypogene minerals in the deposit include pyrite, chalcopyrite, magnetite, molybdenite, and bornite. Supergene enrichment is irregularly developed in the Chah-Firouzeh deposit. Zircon U–Pb dating of two representative samples from the Chah-Firouzeh porphyry stock yielded emplacement ages of 16.9 ± 0.4 Ma and 16.5 ± 0.2 Ma, respectively. The Early-Middle Miocene epoch marks the most important period of porphyry Cu mineralization in the KCMA. During this period, many adakitic magmas intruded the Eocene volcano-sedimentary sequences and formed some of the largest porphyry copper deposits in Iran, such as Sarcheshmeh and Meiduk. Molybdenite Re–Os dating on two samples separated from “B and D type” veinlets show that mineralization occurred at 16.60 ± 0.06 Ma and 15.99 ± 0.06 Ma, implying a time span of about 0.6 Ma for mineralization. The δ^(34)S values for molybdenite, chalcopyrite, and pyrite from “A, B, and D type” veinlets vary from −1.4 to +2.5‰ suggesting a magmatic source for sulfur. The calculated temperatures for sulfide pairs are compatible with those obtained from fluid inclusion microthermometry and show isotope equilibrium due to fluid evolution.

The final publication is available at Elsevier via https://doi.org/10.1016/j.chemgeo.2017.03.015 © 2017. This manuscript version is made available under the CC-BY-NC-ND 4.0 license

Multiple sulfur isotopes provide a powerful tool to study photochemical and biological processes controlling the Archean sulfur cycle and infer related atmospheric and marine environments. However, our understanding of early Earth’s environment remains limited by the availability of well-preserved geological samples, as most Archean sedimentary rocks have experienced some degree of metamorphic alteration. To evaluate sulfur isotopic behavior during post-depositional processes and elucidate the sulfur cycle at 2.7 Ga, we use high-resolution in situ analytical techniques (EPMA and SIMS) to determine elemental compositions and multiple sulfur isotopic compositions of large diagenetic pyrite nodules and fine-grained secondary pyrite disseminated in quartz veins (formed during a lower greenschist metamorphic event) in shales from the 2.7 Ga Joy Lake sequence in the southwest Superior Province. Results show that trace metals and sulfur in the secondary pyrite were derived from both metamorphic fluid and pre-existing diagenetic pyrite. Diagenetic pyrite nodules could have been partially dissolved by metamorphic fluid. But the surviving nodules show elemental and isotopic features different from those of the deduced metamorphic fluid endmember, suggesting the nodules were not geochemically altered by metamorphism, and thus preserve primary isotopic signatures acquired during diagenesis. The sulfur isotopic ratios of pyrite nodules show strong variations, with decreasing δ 34 S values and increasing Δ 33 S values from cores to rims. This negative Δ 33 S–δ 34 S relationship is different from the commonly observed ‘Archean reference line’ defined by most Archean pyrite data, but similar to the ‘felsic volcanic array’. Our observation provides a first possible case from 2.7 Ga, the age of peak crustal growth in the Archean, to support the hypothesis that photochemical pathways could be different under conditions of intense volcanic emission. This study also shows that high-resolution SIMS and EPMA analyses are a robust method for distinguishing primary geochemical signatures from post-depositional alteration, and thus may be used to evaluate the sulfur cycle in Archean sedimentary rocks with low-grade metamorphic overprints.

Re–Os isochron ages for black shales of the Hekkingen Formation in the Barents Sea constrain the onset ( 157.7 ± 1.3 Ma ) and termination ( 138.8 ± 1.0 Ma ), and thereby indicate a long duration (∼19 Myr) of widespread Jurassic–Cretaceous anoxia in the Arctic. Integration of these new Re–Os ages with published radiometric ages, ammonite biostratigraphy and geomagnetic polarity chrons shows shorter late Oxfordian–late Kimmeridgian and longer Berriasian stages relative to estimates in the 2012 and 2016 Geological Time Scales. Late Jurassic anoxia was likely the result of warming climate due to high atmospheric CO2 levels from increased oceanic crust production. Rising temperatures enhanced weathering and nutrient supply, increased productivity, and slowed ocean circulation before a sea-level rise brought anoxic waters onto continental shelves. Assessment of new and published Os- and Sr-isotopic data suggests that prolonged oceanic anoxia required a sustained CO2 source from fast spreading rates and/or longer subduction zones and spreading ridges to balance large burial of carbon in voluminous Upper Jurassic and Lower Cretaceous black shales.

The National Institute of Science and Technology (NIST) research material (RM) 8505 is a Venezuelan crude oil certified for its vanadium concentration. It has recently been proposed as a matrix-matched standard for interlaboratory comparison of Re-Os isotopic analyses while serving as a benchmark for petroleum-based Re-Os method development. Here, the NIST RM 8505 oil is characterized using a multi-solvent asphaltene precipitation, permitting interlaboratory Re-Os data comparison and evaluation of techniques used to derive Re-Os isochron ages. We present a detailed discussion of analytical blank sources, critical evaluation of analytical uncertainties, method improvements and data corrections. Additionally, we provide a comprehensive discussion on the effect of data population size and analytical uncertainty on isochron statistics and the robustness of isochron ages. In addition to NIST RM 8505 (2.43 ± 0.15 ng/g Re, 30.0 ± 0.7 pg/g Os), we provide the first Re-Os data for NIST SRM 1634c (1.73 ± 0.01 ng/g Re, 32.5 ± 0.8 pg/g Os) and EnviroMAT SCP Science (39 ± 1 pg/g Re, 1.01 ± 0.02 pg/g Os), two other commercially available hydrocarbon trace metal standards. The application of several asphaltene (ASPH) precipitations using different n-alkane solvents (pentane, heptane and decane) for the NIST RM 8505 significantly improved the spread of data in the 187Re/188Os-187Os/188Os space. Multi-solvent asphaltene precipitations yield an asphaltene-only Model 1 isochron (75 ± 24 Ma) and the maltene-crude oil-asphaltene triplets yield a more precise Model 1 isochron age of 78.5 ± 2.3 Ma with a 187Os/188Osinitial of 0.877 ± 0.021. Our age is considerably older compared to a previously reported Model 1 age of 62.7 ± 5.7 Ma based on C7 ASPH-crude oil-MALT triplets ( Liu and Selby, 2017 ) and considerably younger than the Model 1 age of 98.4 ± 9.5 Ma based on ASPH separates ( Liu et al., 2019 ). The analytical reasons leading to these age differences are discussed in this paper. The geological context for the NIST 8505 oil is unknown, therefore we use trace metal data (Ni, V, Fe, Mo, etc.) to derive plausible constraints for the origin of this oil. The NIST 8505 oil shows trace metal data similar to published data for oils from the Urdaneta district, the La Paz, Mara and Lagunillas oil fields and source rocks of the La Luna Formation in the Maracaibo Basin, Venezuela. In this geological context, our ~79 Ma age for the NIST 8505 oil implies a Late Cretaceous early hydrocarbon generation event from older Upper Cretaceous source rocks and overlaps with the youngest age of potential source rocks in the Maracaibo Basin. However, the age of large-scale oil generation in the Maracaibo Basin is significantly younger, lasting from the Oligocene to the Pliocene.

Coal deposits are integral to understanding the structural evolution and thermal history of sedimentary basins and correlating contemporeous estuarine and fluvial delatic strata with marine sections. While marine shales may readily lend themselves to Re–Os dating due to the dominance of hydrogenous Re and Os, the lack of a chronometer for near-shore sedimentary environments hampers basinwide correlations in absolute time. Here, we employ the Re–Os geochronometer, along with total organic carbon (TOC) and Rock–Eval data, to determine the timing and conditions of a marine incursion at the top of the Matewan coal bed, Kanawha Formation, Pottsville Group, West Virginia, USA. The observed range for hydrogen index (HI: 267–290 mg hydrocarbon/gram total organic carbon) for these coal samples suggests dominance of aliphatic hydrocarbons with low carbon ( 107.6 ± 16.4 ng / g ) and Os ( 0.52 ± 0.09 ng / g ) concentrations of the marine-influenced Matewan coal are higher by few orders of magnitude than published data for terrestrial coal. A Re–Os isochron for the Matewan coal provides an age of 325 ± 14 Ma (Model 3; MSWD = 12; n = 19 ; 2σ). This is the first Re–Os age derived from coal samples; the age overlaps a new composite Re–Os age of 317 ± 2 Ma for the immediately overlying Betsie Shale Member. External precision for replicate Os analyses carried out for several Matewan coal samples shows a positive correlation with their HI. The HI, which is low in terrestrial organic matter, reflects the degree of marine influence. Thus, samples with the most profound marine influence also have the best analytical reproducibility. Equilibration of Os isotopes with seawater under marine conditions overwhelms variability inherited from terrestrial plant debris, decreasing scatter on the isochron. The 187Re/188Os ratios of the Matewan coal (∼3300–5135) are higher than most of those previously published for Phanerozoic black shale (mostly

The Palaeoproterozoic Yerrida, Bryah and Padbury Group sedimentary rocks are located on the northern margin of the Archaean Yilgarn Craton and are host to epigenetic gold (Peak Hill, Fortnum and Horseshoe), volcanic-hosted massive sulphide (VHMS; Horseshoe Lights, Red Bore and DeGrussa) and epithermal copper deposits (Thaduna). The DeGrussa Cu–Au–Ag VHMS deposit (12.4 Mt @ 4.7% Cu and 1.8 g/t Au) comprises four lenses and is hosted in turbiditic sedimentary rocks and basalts of the DeGrussa host sediments/Karalundi Formation, the lowest mafic volcano-sedimentary unit of the Bryah Group and crosscut by intrusive dolerite of Narracoota Formation age. Immediate wall rocks to the ore lenses are commonly altered to chlorite and talc-carbonate. A number of geochronological techniques were employed to date mineralisation in the DeGrussa deposit. These include rhenium–osmium (Re–Os) of molybdenite, Pb isotopes of galena and pyrite, and U–Pb on zircon. Re–Os geochronology of molybdenite resulted in ages of 2027 ± 7 Ma and 2011 ± 7 Ma and 2013 ± 7 Ma for mineralisation, similar to Pb–Pb model ages for galena of 2060 ± 50 Ma and 2075 ± 50 Ma. U–Pb for magmatic zircons from intrusive dolerite within the mine sequence provided ages of 1991 ± 7 Ma, 1999 ± 7 Ma and 2003 ± 7 Ma with granodiorite rocks providing ages of 2014 ± 7 Ma and 2018 ± 9 Ma. Remobilisation of DeGrussa sulphides occurred at approximately 1980 Ma given Re–Os ages of pyrrhotite (1982 ± 7 Ma and 1984 ± 8 Ma) and Pb–Pb pyrite ages of 1980 ± 30 Ma. Re-examination of the Pb isotopic evolution models for this area and the Capricorn Orogen suggests that the model of Stacey and Kramers (1975) is more appropriate than Cumming and Richards (1975) ; using the former model leads to revised model ages as follows: Horseshoe Lights VHMS 2000 ± 35 Ma; Nathans 1820 ± 30 Ma, Peak Hill (Main pit: 1610 Ma, 1620 Ma, 1705 Ma, and 2070 ± 30 Ma; Fiveways: 1955 Ma; Mt. Pleasant: 1770 Ma), Horseshoe/Cassidy 1940 ± 30 Ma, Mikhaburra 1915 ± 30 Ma, and Labouchere 1800 ± 30 Ma. These new ages coincide with major regional orogenic events – the Glenburgh from 2005 to 1960 Ma, the Capricorn from 1830 to 1780 Ma, the Mangaroon from 1690 to 1620 Ma, and the Edmundian from 920 to 850 Ma. Although orogenic events are compressional, the Yerrida/Bryah Group sedimentary rocks, along with mineralisation at the DeGrussa and Horseshoe Lights deposits, were formed in an extensional basin setting during the Glenburgh Orogeny. These new ages assist in constraining stratigraphic and mineralising events of the Palaeoproterozoic Yerrida, Bryah and Padbury Group with regional orogenic events and may provide guidance for exploration for significant gold and base metal mineralisation, not only in the Bryah, but also throughout the larger Capricorn Orogen.

Re-Os dating of three samples of hydrothermal molybdenite collected from the Pueblo Viejo Au-Ag-Cu district (5.5 Moz gold, past production, 16.2 Moz proven plus probable gold ore reserves) yields ages of 112.1 ± 0.4, 112.0 ± 0.4, and 111.5 ± 0.4 Ma. These Re-Os dates confirm an Early Cretaceous age for mineralization, coeval with tholeiitic, intraoceanic island arc volcanism and, in particular, with an episode of felsic magmatism and extension across the Early Cretaceous arc (110–118 Ma). Re-Os dating of a sample of hydrothermal molybdenite collected from the Douvray porphyry Cu-Mo deposit (with inferred resources of 1,257 Mlb Cu, 0.276 Moz Au, 6.84 Moz Ag, and 4,367 tons Mo) yields an age of 93.3 ± 0.3 Ma, coeval with calc-alkaline magmatism along the Greater Antilles island arc.

The geochemical record for the Permian–Triassic boundary in northern latitudes is essential to evaluation of global changes associated with the most profound extinction of life on Earth. We present inorganic and organic geochemical data, and Re–Os isotope systematics in a critical stratigraphic interval of pre- and post-extinction Upper Permian–Lower Triassic sediments from Opal Creek, western Canada (paleolatitude of ∼30°N). We document significant and long-lived changes in Panthalassa seawater chemistry that were initiated during the first of four magmatic or meteoritic inputs to Late Permian seawater, evidenced by notable decreases of Os isotopic ratios upsection. Geochemical signals indicate establishment of anoxic bottom waters shortly after regional transgression reinitiated sedimentation in the Late Permian. Euxinic signals are most prominent in the Upper Permian sediments with low organic carbon and high sulfur contents, and gradually wane in the Lower Triassic. The observed features may have been generated in a strongly euxinic ocean in which high bacterioplankton productivity sustained prolific microbial sulfate reduction in the sediment and/or water column, providing hydrogen sulfide to form pyrite. This scenario requires nearly complete anaerobic decomposition of predominantly labile marine organic matter (OM) without the necessity for a complete collapse of primary marine productivity. Similar geochemical variations could have been achieved by widespread oxidation of methane by sulfate reducers after a methanogenic burst in the Late Permian. Both scenarios could have provided similar kill mechanisms for the latest Permian mass extinction. Despite the moderate thermal maturity of the section, OM in all studied samples is dominantly terrestrial and/or continentally derived, recycled and refractory ancient OM. We argue that, as such, the quantity of the OM in the section mainly reflects changes in terrestrial vegetation and/or weathering, and not in marine productivity. At Opal Creek, a pyrite layer and

Earth's most extreme extinction event near the end of the Late Permian decimated more than 90% of all extant marine species. Widespread and intensive oceanic anoxia almost certainly contributed to the catastrophe, though the driving mechanisms that sustained such conditions are still debated. Of particular interest is whether water column anoxia was a consequence of a ‘stagnant ocean’, or if it was controlled by increases in nutrient supply, primary productivity, and subsequent heterotrophic respiration. Testing these competing hypotheses requires deconvolving sedimentary/bottom water redox conditions from changes in surface water productivity in marine sediments. We address this issue by studying marine shales from East Greenland and the mid-Norwegian shelf and combining sedimentary redox proxies with cadmium-isotopic analyses. Sedimentary nitrogen-isotopic data, pyrite framboid analyses, and organic and inorganic shale geochemistry reveal sulfidic conditions with vigorous upwelling, and increasingly anoxic conditions with a strengthening upwelling in the Greenland and Norwegian sections, respectively. Detailed analysis of sedimentary metal budgets illustrates that Cd is primarily associated with organic carbon and records primary geochemical signatures, thus enabling reconstruction of surface water nutrient utilization. Cadmium-isotopic analyses of the authigenic shale fraction released by inverse aqua regia digestion yield an average δ Cd 114 / 110 of + 0.15 ± 0.01 ‰ (2 SE, n = 12 ; rel. NIST SRM 3108), indicative of incomplete surface water nutrient utilization up-section. The constant degree of nutrient utilization combined with strong upwelling requires increasing primary productivity – and not oceanic stagnation – to balance the larger nutrient fluxes to both study sites during the development of the Late Permian water column anoxia. Overall, our data illustrate that if bottom water redox and upwelling can be adequately constrained, Cd-isotopic analyses of organic-rich sediments can be used to provide valuable information on nutrient utilization and therefore past productivity.

Hosted in the Early Cretaceous bimodal tholeiite volcanic series of the Los Ranchos Formation, the Dona Amanda and Cerro Kiosko deposits in the Bayaguana district represent significant Au, Cu, and Ag resources in the Cordillera Oriental of the Dominican Republic. At Dona Amanda, a dense stockwork of quartz-sulfide veins is hosted by volcanic rocks with intense transitional phyllic-advanced argillic and silicic hydrothermal alteration assemblages, indicating a high-sulfidation environment. Wavy quartz veins with central sutures and rims of pyrite + enargite + molybdenite + fahlore (B veins) are cut by planar quartz-pyrite D veins. Primary fluid inclusions in quartz from B veins (Th: 160°–>400°C; salinity: 7.9–16.4 wt % NaCl equiv) are interpreted as porphyry-type fluids. Inclusion fluids in quartz of quartz-pyrite veins (Th: 125°–175°C; salinity: 4.8–12.2 wt % NaCl equiv), quartz from silicic altered wall rocks (Th: 150°–175°C; salinity: 8.3–13.9 wt % NaCl equiv), and late, distal calcite veins (Th: 120°–160°C; salinity: 5.0–13.3 wt % NaCl equiv) indicate limited mixing with more dilute fluids and rule out mixing with fresh meteoric water. In Cerro Kiosko, a swarm of fault-controlled massive chalcopyrite + enargite + bornite + fahlore D veins and lodes are hosted by rocks with pervasive kaolinite alteration after sericite. δ 34S values of vein sulfides from both deposits are all close to −2‰ and consistent with a predominance of magmatic sulfur and sulfide deposition from an oxidizing magmatic fluid. These data are consistent with a transitional environment between a deeper porphyry Cu(-Mo) and an overlying high-sulfidation epithermal deposit. An Re-Os age (112.6 ± 0.4 Ma) for molybdenite from the Dona Amanda deposit places the porphyry-epithermal mineralization as Early Cretaceous, coeval with the Los Ranchos Formation host rocks and with the Pueblo Viejo deposit. New sensitive high-resolution ion microprobe U-Pb ages on zircons from plagioclase-phyric rhyolite domes in the Bayaguana district are consistent with porphyry–high-sulfidation epithermal mineralization occurring along the Los Ranchos Formation during tonalite batholith emplacement in the basaltic island-arc basement at ca. 118 to 112 Ma and finalization of felsic volcanism at ca. 110 to 107 Ma.

The Enterprise nickel deposit (40 Mt of 1.07% Ni) is located on the eastern edge of the Kabompo dome in the North-Western Province of Zambia. The deposit area contains basement schists overlain by Neoproterozoic metasedimentary rocks. Nickel sulfides are hosted within a sequence of quartz-, carbonate-, and carbon-rich metasedimentary rocks that interfinger with and overlie siliciclastic metasedimentary rocks. The host rocks contain significant kyanite, talc, and magnesian chlorite. Silicification and magnesian metasomatism occurred prior to or concurrent with a regional metamorphic event (590–500 Ma). Mineralization resulted in the precipitation of nickel and iron-nickel sulfides in veins and as semimassive replacements of the host rocks. Nickel sulfides precipitated in two main stages: a millerite-vaesite-pyrite assemblage that formed disseminations and semimassive replacements in vuggy textured rocks, and a later millerite-bravoite-(molybdenite) assemblage in quartz-kyanite veins and local semimassive replacements. The deposit contains minor copper and trace amounts of cobalt and platinum group elements (PGEs). A discrete zone of copper sulfides underlies a portion of the nickel sulfide zone. Re-Os geochronology on molybdenite yields a 540.6 ± 1.8 Ma age for mineralization at Enterprise, the approximate age of metamorphism. Sulfur isotope results indicate that the sulfur at Enterprise was derived largely from Neoproterozoic marine sulfate by thermochemical sulfate reduction. Significant volumes of mafic igneous rocks are not present in the immediate area of the Enterprise deposit. No evidence of prealteration concentrations of nickel exists within the sedimentary rock sequence at the deposit. The alteration and mineralization style of the Enterprise deposit is similar to the much less metamorphosed nickel-bearing Shinkolobwe uranium deposit in the Democratic Republic of Congo (DRC), though the Enterprise deposit does not contain significant uranium. The sediment-hosted nickel-rich deposits of Central African Copperbelt exemplified by Enterprise appear to represent a new style of hydrothermal nickel mineralization.

The pilot study with Re–Os dating of sulfides from Sukhoi Log and Olympiada gold deposits revealed early Paleozoic ages of the auriferous sulfides from the two largest orogenic gold systems in the Neoproterozoic orogens of the Baikalides framing the Siberian craton. The age-dating results indicate that gold mineralization is therefore epigenetic. The formation of the dated orogenic gold deposits is synchronous with some regional metamorphic events in the Baikalides, at least in case of the Sukhoi Log deposit. The metamorphic events occurred in the rear parts of the early Paleozoic magmatic arcs, where coeval subduction-related magmatism produced porphyry copper–(molybdenum) mineralization.

Chemical and isotopic signatures for black shales serve as potential proxies for reconstruction of paleoenvironmental conditions. Here we bring Rock-Eval, major and trace element and Re-Os isotopic data together to examine the environmental record at the Cambrian-Ordovician Global Stratotype Section and Point (GSSP) at Green Point in western Newfoundland, Canada. The Green Point shales are oil mature and contain Type II organic material of marine origin. A Re-Os isochron for the shales provides the first radiometric age for shale deposition at the GSSP at 484 ± 16 Ma, with an initial 187Os/188Os ratio of 0.74 ± 0.05 (Model 3 age; MSWD = 21; n = 13; 2σ uncertainties). Factor analysis of the geochemical data set shows association of most trace elements with total organic carbon (TOC) and S contents, ensuring an authigenic origin for most elements and hence, their validity for evaluating the paleo-redox state. Relatively high-enrichment factors for redox-sensitive elements (e.g., Re, U, and Mo) compared to average shale, but comparatively low enrichment compared to modern Black Sea sediments, suggest deposition in anoxic, but not euxinic waters. Comparison of Lower Ordovician shale geochemistry data sets at a global scale leads us to suggest that anoxic conditions and warm oceanic regimes were restricted to the margins of Laurentia and Baltica, whereas depositional basins with colder waters (e.g., Avalonia and Gondwana) were less reducing. These outcomes underscore the important role of paleogeography in regulating oceanic conditions and marine life.

Sulfide minerals from the El Salvador porphyry Cu–Mo deposit, Chile, were dated by Re–Os geochronology to clarify the timing and duration of mineralization. As these data are collected over the past 10 years, they chronicle the evolution of Re–Os analytical procedures and improvements in spike-sample equilibration, mass spectrometry and data reduction. Included in the data is the first tennantite–pyrite Re–Os isochron along with tennantite–enargite–pyrite Os tracing of ore metals based on initial osmium systematics (187Os/188Osi). Porphyry-associated mineralization follows the traditional early (A), transitional (B), and late (D) stage classification of relative timing of vein formation. Most Cu- and Mo-bearing sulfides were deposited during stages A and B. Field relationships clearly show the B-stage veins are older than the D-stage veins. Samples analyzed with Carius tube digestion and mixed-double spike indicate B-stage molybdenite mineralization between 41.8 and 41.2 Ma. These ages best represent the timing of main-stage mineralization at El Salvador. A five-point 187Re–187Os isochron for pyrite–tennantite from the latest D-stage veins yields an age of 42.37 ± 0.45 Ma. The isochron age, while older, is within error of early analyses of molybdenite by alkaline fusion digestion using single Re and Os spikes (42.4–42.0 Ma). A separate pyrite and tennantite–enargite pair containing significant common Os yields an initial 187Os/188Os ratio of 0.134 ± 0.042, compatible with a predominantly mantle origin. We appreciate the early analyses for their historical significance while emphasize the geological implications of the 41.8–41.2 Ma molybdenite ages. Temperature estimates by sulfur thermometry and fluid inclusions are 390–510 °C for the B-stage molybdenites and 230–240 °C for the latest D-stage pyrite and tennantite. Analyses based on Carius tube digestion and updated spike calibrations suggest a ∼0.6 m.y. duration (∼41.8 to 41.2 Ma) in-line with published deposit geochronology. The timing and duration of mineralization from Re–Os dating of ore minerals is more precise than estimates from previously reported 40Ar/39Ar and K–Ar ages on alteration minerals. The Re–Os results suggest that the mineralization is temporally distinct from pre-mineral rhyolite porphyry (42.63 ± 0.28 Ma) and is immediately prior to or overlapping with post-mineral latite dike emplacement (41.16 ± 0.48 Ma). Based on the Re–Os and other geochronologic data, the Middle Eocene intrusive activity in the El Salvador district is divided into three pulses: (1) 44–42.5 Ma for weakly mineralized porphyry intrusions, (2) 41.8–41.2 Ma for intensely mineralized porphyry intrusions, and (3) ∼41 Ma for small latite dike intrusions without major porphyry stocks. The orientation of igneous dikes and porphyry stocks changed from NNE-SSW during the first pulse to WNW-ESE for the second and third pulses. This implies that the WNW-ESE striking stress changed from σ3 (minimum principal compressive stress) during the first pulse to σHmax (maximum principal compressional stress in a horizontal plane) during the second and third pulses. Therefore, the focus of intense porphyry Cu–Mo mineralization occurred during a transient geodynamic reconfiguration just before extinction of major intrusive activity in the region.

[1] The Questa porphyry Mo deposit in New Mexico provides a unique opportunity to study the relationship between pluton assembly and mineralization in a long-lived volcanic field. Magmatism along the caldera margin initiated at ~ 25.20 Ma and continued for ~ 770 ka. During this time, the emplacement of mineralizing intrusions progressed westward and culminated in the assembly of the Questa Mo deposit between 24.76 Ma and 24.50 Ma. Molybdenite Re/Os geochronology shows that mineralization occurred in multiple pulses without thermal resetting of the chronometer. Because most of the molybdenite samples used in this study are from previous fluid inclusion studies, we treat Re/Os molybdenite as a new thermochronometer. Molybdenite Re/Os ages are integrated with zircon U/Pb ages to evaluate the cooling histories within the Mo deposit. This study suggests that individual cycles of magma emplacement and mineralization cooled rapidly. In contrast to prior genetic models for the Questa Mo deposit, these data show that the mineralizing intrusions were generated via rapid melt generation, separation, and intrusion into the shallow crust without involvement in a long-lived magma chamber. It is proposed that the anomalously high magma flux event associated with ignimbrite eruption transferred materials (Mo, volatiles) from the upper mantle necessary for immediately subsequent mineralization. Partial melting and scavenging within a deep-crustal hybridized zone generated Mo-rich magma that ascended to form the Questa deposit. Moreover, this hypothesis predicts an important connection between caldera-forming systems and porphyry-style mineralization that could be incorporated into future exploration models.

Temporal trends in Earth's near-surface mineralogy correlate with major events in Earth's geochemical and tectonic history. New and published analyses of 422 molybdenite (MoS2) specimens from 135 localities with known ages from 2.91 billion years (Ga) to 6.3 million years (Ma) reveal two statistically significant trends. First, systematic increases in average and maximum trace concentrations of Re in molybdenite since 3.0 Ga point to enhanced oxidative weathering by subsurface fluids. In addition, episodic molybdenum mineralization correlates with five intervals of supercontinent assembly from ∼2.7 Ga (Kenorland) to 300 Ma (Pangaea).

The Mirador porphyry Cu-Au district is located in the southernmost sector of the northern Andean Cordillera, in Zamora-Chinchipe province, southeastern Ecuador. The district contains two significant porphyry Cu-Au ± Ag ± Mo deposits, Mirador and Mirador Norte, and an interconnected series of narrow, mineralized structures known collectively as Chancho. The principal mineralization in the porphyries is disseminated to blebby chalcopyrite developed primarily in potassic alteration, with overlying chalcocite supergene enrichment zones. Prior to radiometric dating presented in this study, these deposits were considered Late Jurassic based on close similarity, and therefore assumed age equivalence, with the well-dated Panantza, San Carlos, and Sutzu porphyry copper deposits located 40 km to the north. New U-Pb zircon ages confirm a Middle Jurassic age for granodiorite of the Zamora batholith at this location (163.8 ± 1.9 Ma), and Late Jurassic ages for subvolcanic intrusions (156.2 ± 1.0 and 153.1 ± 1.3 Ma). Re-Os molybdenite ages average 156 ± 1.0 Ma and indicate coeval mineralization between Mirador and Mirador Norte. Mineralization and related sub-volcanic igneous activity are closely associated at Mirador and represent the same temporal event recorded at Panantza-San Carlos and Sutzu, as well as coeval porphyry, skarn, and epithermal Au mineralization extending at least 80 km south, defining a north-south Cu-Au metallogenic belt spanning over 120 km.

Re and Os isotopes in shales are increasingly used for precise and accurate geochronology and for tracking rates of continental weathering in the geologic past. Moreover, trace element compositions of organic-rich shales reveal paleoredox conditions and properties of shale organic matter (OM) useful for lithostratigraphic correlations. Chemical weathering alters the original shale composition and hence may compromise geologic interpretations based on geochemical data. Here we compare Re–Os isotopes, trace elements and OM properties in correlative shales from outcrops and nearby drillcore to quantify the effects of weathering. We define chemical parameters that distinguish weathered from pristine shale in samples that are macroscopically identical. Black shale from the Ravnefjeld Formation in East Greenland yields disturbed Re–Os isotope systematics for outcrop samples, and highly precise Re–Os isochron ages for drillcore. Geochemical data show that Re, Os and common Os are hosted in the organic matter rather than sulfides. Re and Os both show mobility during weathering. Combined use of Rock-Eval pyrolysis indices and sulfur contents documents oxidation of both OM and pyrite, thereby providing a valuable chemical criterion to assess invisible shale weathering. Further studies on chemically diverse shales will test the widespread application of these criteria as weathering indicators. Systematic differences in major and trace element content and kerogen quality between weathered and fresh shale samples are used to characterize and quantify weathering effects. The character of the OM in shales is most telling. Ravnefjeld data are compared with data from time correlative shales from the mid-Norwegian shelf [Georgiev et al., 2011. Hot acidic Late Permian seas stifle life in record time. Earth Planet. Sci. Lett., 310, 389–400] to present a strategy for identification of Re–Os isochroneity in advance of Re–Os analytical work. Our recent compilation and comparison of Upper Permian shales from widely separated sequences on Pangea's margins reveal exceptionally high Re/Os ratios on a global scale. We suggest Upper Permian shales may have significantly influenced the Cenozoic (e.g. Eocene) 187Os/188Os ratio of seawater on their exposure and weathering.

Trace elements such as U, Mo, Re, V and Ni in marine shales are commonly used to probe paleoenvironmental conditions. Trace elements may have either a detrital or seawater source, or both. The seawater contribution is often modelled from whole-rock sediment analyses. Using whole-rock trace element ratios as paleoredox proxies, however, presents limitations. In this study, we compare three different methods of digestion using Middle Triassic black shales from Svalbard and Svalis Dome, and Late Permian black shales from the mid-Norwegian shelf and East Greenland. Multi-acid total digestion provides whole-rock compositions, including both detrital and seawater contributions. Aqua regia and inverse aqua regia digestions dissolve organic matter, sulfides and carbonates, leaving behind major detrital silicate components. Thus, trace element concentrations by aqua regia digestion provide a direct, though still imperfect approximation of the seawater component. For most trace elements, the concentrations and their ratios derived from aqua regia and inverse aqua regia digestions agree within 10%, roughly the uncertainty of the analytical procedures. However, inverse aqua regia may not dissolve apatite completely, which leads to slightly lower Ca, P, Sc, U and Pb contents than aqua regia digestion. Multi-acid whole-rock total digestion and aqua regia partial digestion yield comparable abundances of P, S, Co, Ni, Cu, Zn, Mn, Mo and Pb, which are dominantly of seawater origin in our samples. However, concentrations of U, V, Sc and Cr derived from aqua regia digestion are up to 80% lower than those from whole-rock digestion, suggesting significant contributions from both detrital and seawater sources. We conclude that: (1) trace metals released by aqua regia or inverse aqua regia predominantly reflect seawater components, and thus have value as paleoredox proxies, (2) if the absolute trace metal concentrations are used to infer the paleoredox conditions, the total amount of organic carbon and sulphur must be taken into account, and (3) threshold values for trace metal ratios based on whole-rock compositions (e.g., Th/U, V/Sc, V/V + Ni) are not globally applicable to infer redox conditions, as these ratios reflect a combination of both detrital and seawater components.

The end of Permian time (252–251 Ma) hosts the largest mass extinction in Earth history, yet events heralding this global catastrophe remain intensely disputed. We present a chemostratigraphic marker, the 187Re/188Os ratio, which soars to unprecedented levels approaching the Permo-Triassic boundary. These ratios are tied to profound trace element changes and a precise Re–Os time record at 252 Ma preserved in black shales from East Greenland and the mid-Norwegian shelf. Within a 36-meter shale section, an 80-fold increase in Re concentrations (two-fold for Os) signals seawater conditions that became increasingly inhospitable to life. Unwavering initial 187Os/188Os ratios of 0.6 preclude mafic volcanism and meteorite impact as the direct cause of Late Permian anoxia. We argue that extraordinarily high 187Re/188Os ratios are the hallmark of simultaneously rising ocean temperature and acidity, leading to loss of oxygen and the stifling of life in latest Permian time.

The age of the hydrothermal Co-Ni-As-(Au) mineralization in the Bou Azzer-El Graara inlier was determined using different isotopic systems on ore and mineralization-related gangue minerals, namely Re-Os on molybdenite, Sm-Nd on carbonates, and U-Pb on brannerite. Re-Os dating of molybdenite was difficult owing to the intimate intergrowth of molybdenite with Co arsenides and the fact that sampling by drilling complex sulfide mixtures resulted in poor concentration of molybdenite. Accordingly, Re-Os dating of the impure molybdenite-sulfide mixtures yielded inconsistent ages in the range 400 to 350 Ma. This scatter is attributed to (1) inadequate concentration of pure molybdenite, (2) complex Re-Os systematics, possibly involving excess radiogenic Os derived from older generation(s) of sulfide, and/or (3) mixture of at least two Re-Os systems consisting of a component with pre-Hercynian history and later disturbance by Hercynian metamorphism. Carbonates and brannerite that coexist with molybdenite gave more consistent ages of 308 ± 31 Ma (Sm-Nd) and 310 ± 5 Ma (U-Pb), respectively. Because both ages agree within their errors, we regard the brannerite U-Pb age of 310 ± 5 (2σ) Ma as the best and most precise estimate for the age of the Co-Ni-As-(Au) mineralization. Although an earlier onset of mineralization cannot be ignored totally, the new age data underline that the principal Co-Ni-As-(Au) mineralization at Bou Azzer occupying the main ore-bearing structures was driven by and formed during the end of the Hercynian orogeny.

Rhenium–osmium (Re–Os) dating of carbonaceous rocks using H 2 SO 4 -CrO 3 dissolution provides a powerful new geochronologic tool for Archean terranes. Here we document the oldest Re–Os depositional ages yet reported for carbonaceous sedimentary rocks. Carbonaceous slates are intercalated with graywackes and mafic tuffs of the Joy Lake sequence in the western Wawa subprovince of the Superior Province. Well-developed D 2 cleavage is sub-parallel to bedding. Pyrite occurs in nodules, disseminations, and bedding-parallel stringers. Samples from two drill holes (DH26503 and DH26506) yield isochron ages of 2695 ± 14 Ma and 2684 ± 16 Ma and initial 187 Os/ 188 Os ratios (Os i ) of 0.15 ± 0.16 and − 0.29 ± 0.20, respectively. The ages, identical within uncertainty, provide the first temporal constraints for the westernmost Wawa subprovince greenstone sequence. The ages are consistent with cessation of mafic/ultramafic volcanism before ca. 2695 Ma in the western Wawa subprovince and D 2 deformation before 2685 Ma farther east. The Joy Lake sequence is likely the temporal equivalent of turbiditic graywackes deposited further east, both sourced from arc volcanoes during collision of the Wawa and Wabigoon arcs along the southern margin of the Superior Province. A chondritic Os i (0.109 at 2.69 Ga) is expected for Archean shales, but the negative Os i for DH26506 requires explanation. Re, which is significantly more mobile than Os, may have been released from intercalated high-Re/Os mafic tuffs by local oxidation during recent or Cretaceous exposure to meteoric waters. The adjacent carbonaceous rocks are a ready sink for mobile Re. A small Re addition can shift isochron data points to higher 187 Re/ 188 Os ratios with minimal slope change. This increases scatter and uncertainty for the Os i , shifts the isochron to the right, and produces a spuriously low Os i intercept. If Re addition is recent, the age is not significantly affected. Notably, the slates in DH26506 which yield the negative Os i are intercalated with relatively permeable and reactive lithic wackes and mafic tuffs, whereas the slates in DH26503 are in contact with less permeable massive intrusive rocks. This process can be detected only if the true Os i is approximately chondritic, and is more likely where reactive mafic rocks are prevalent—both the case for Archean greenstone belts.

The Hilltop, Lewis, and Bullion mining districts, located within the northern Shoshone Range, Lander County, Nevada, are part of the greater Battle Mountain-Eureka trend. Historic production of mostly Ag with Au, Cu, Pb, and Zn from all three districts exploited ≤ 3-m-wide quartz veins hosted mainly within upper plate Ordovician-Devonian siliceous and siliciclastic rocks of the Roberts Mountains allochthon. Eocene felsic intrusive rocks, located both proximal and distal to the vein deposits, were emplaced throughout the northern Shoshone Range along a west-northwest trend; molybdenite mineralization is associated with some intrusive rocks, and some intrusive rocks host vein-type mineralization. New and previously published radiometric ages for primary igneous minerals from unaltered rocks within and/or proximal to mineralized areas are nearly coincident with published Re-Os ages for several northern Shoshone Range molybdenite occurrences (40.1 ± 0.6 Ma, avg), supporting a relationship between pluton emplacement and molybdenite mineralization. Age differences between quartz vein-hosted gold ± base metal mineralization (e.g., 38.3 ± 0.1 Ma: Gray Eagle mine, Bullion district) and nearby intrusive rocks (e.g., 39.0 ± 0.1 Ma: Granite Mountain) imply that vein mineralization probably formed during prolonged hydrothermal activity, synchronous with or subsequent to igneous rock emplacement, or from heat associated with a second, slightly younger phase of intrusive igneous activity. Primary fluid inclusion salinity (0–6.4 wt % NaCl equiv) and Th (115°–425°C) data from ore-bearing vein quartz, in conjunction with measured δ18OVSMOW data (−0.97 to +17.3‰), indicate that vein-forming fluids contained variable mixtures of magmatic and meteoric components (calculated δ18OVSMOW values of −16.0 to +13.3‰) and spanned the epithermal-porphyry temperature continuum. New and previously published stable isotope (C, O, and S) data from vein-hosted ore and gangue minerals, unaltered and altered siliceous (upper plate) host rocks, and unaltered carbonate (lower plate and upper plate) rocks indicate mixed and variable sources of vein-hosted ore and gangue components and variable interaction between some vein-forming fluids and nonsiliceous rock types (carbonates, bedded barite) that underlie the northern Shoshone Range. Large vein widths, high vein densities, and lack of evidence supporting fluid boiling in primary fluid inclusions suggest that vein deposits of the northern Shoshone Range probably formed at shallow depths (≤1 km) under lithostatic conditions. Geochronology and stable isotope data support a temporal and genetic link between Eocene magmatism, quartz vein-hosted precious and base metal mineralization, and molybdenite (porphyry) mineralization within the Hilltop, Lewis, and Bullion mining districts.

Increasing use of Re–Os geochronology, especially applied to molybdenite, requires a standard for cross-laboratory calibration. A new Reference Material (RM) for Re–Os geochronology, a molybdenite powder acquired from the Henderson mine and mill in Colorado, has been characterized by two independent laboratories using isotope dilution and NTIMS. Following cleaning, the powder was split and bottled by NIST for distribution. Twelve bottles were randomly selected for this study. The AIRIE Program at Colorado State University and the Radiogenic Isotope Facility at the University of Alberta each produced replicate analyses from six of the bottles using two different Os spikes (one enriched in both 188Os and 190Os and one of normal isotopic composition), for a total of 48 analyses comprising four data sets. The age of the new RM is thus defined as 27.656 ± 0.022 Ma (95% conf.). We also address the long-standing issue of the stoichiometry of Os gravimetric standards, produced from ammonium and potassium Os salts. We advocate the use of (NH4)2OsCl6 as the starting material. The actual Os content of this salt can be precisely determined by ignition under an atmosphere of 2% H2/98% N2. Reduction of the salt using a gas of higher H2 content can lead to erroneous determinations of Os content, perhaps because of the formation of osmium hydrides. Furthermore, we show that it is not always correct to assume ideal stoichiometry for K2OsCl6.

The Apuseni–Banat–Timok–Srednogorie magmatic–metallogenic belt (ABTS belt), forms a substantial metallogenic province in the Balkan-South Carpathian system in southeastern Europe. The belt hosts porphyry, skarn, and epithermal deposits mined since pre-Roman times. Generally, the deposits, prospects, and occurrences within the belt are linked to magmatic centers of calc-alkaline affinity. Fifty-one rhenium-osmium (Re–Os) ages and Re concentration data for molybdenites define systematic geochronologic trends and constrain the geochemical-metallogenic evolution of the belt in space and time. From these data and additional existing geologic-geochemical data, a general tectonic history for the belt is proposed. Mineralization ages in Apuseni-Banat, Timok, and Panagyurishte (the central district of the larger E–W Srednogorie Zone) range from 72–83, 81–88, and 87–92 Ma, respectively, and clearly document increasing age from the northwestern districts to the southeastern districts. Further, Re–Os ages suggest rapidly migrating pulses of Late Cretaceous magmatic–hydrothermal activity with construction of deposits in ~1 m.y., districts in ~10 m.y., and the entire 1,500 km belt in ~20 m.y. Ages in both Timok and Panagyurishte show systematic younging, while deposit ages in Banat and Apuseni are less systematic reflecting a restricted evolution of the tectonic system. Systematic differences are also observed for molybdenite Re concentrations on the belt scale. Re concentrations generally range from hundreds to thousands of parts per million, typical of subduction-related Cu–Au–Mo–(PGE) porphyry systems associated with the generation of juvenile crust. The geochronologic and geochemical trends are compatible with proposed steepening of subducting oceanic slab and relaxation of upper continental plate compression. Resulting influx of sub-continental mantle lithosphere (SCML) and asthenosphere provide a fertile metal source and heat, while the subducting slab contributes connate and mineral dehydration fluids, which facilitate partial melting and metal leaching of SCML and asthenosphere. Cu–Au–Mo–(PGE) porphyry deposits may develop where melts are trapped at shallow crustal levels, often with associated volcanism and epithermal-style deposits (South Banat, Timok, and Panagyurishte). Mo–Fe–Pb–Zn skarn deposits may develop where felsic melts are trapped adjacent to Mesozoic limestones at moderate crustal levels (North Banat and Apuseni). Systematic spatial variations in deposit style, commodity enrichment, Re–Os ages, and Re concentrations support specific tectonic processes that led to ore formation. In a post-collisional setting, subduction of Vardar oceanic crust may have stalled, causing slab steepening and rollback. The slab rollback relaxes compression, facilitating and enhancing orogenic collapse of previously thickened Balkan-South Carpathian crust. The progression of coupled rollback-orogenic collapse is evidenced by the width of Late Cretaceous extensional basins and northward younging of Re–Os ages, from Panagyurishte (~60 km; 92–87 Ma) to Timok (~20 km; 88–81 Ma) to Apuseni-Banat (~5 km; 83–72 Ma). Generation of a well-endowed mineral belt, such as the ABTS, requires a temporally and spatially restricted window of magmatic–hydrothermal activity. This window is quickly opened as upper plate compression relaxes, thereby inducing melt generation and ingress of melt to higher crustal levels. The window is just as quickly closed as upper plate compression is reinstated. The transient tectonic state responsible for economic mineralization in the ABTS belt may be a paleo-analogue to transient intervals in the present subduction tectonics of SE Asia where much mineral wealth has been created in the last few million years.

The Rakkurijarvi prospect consists of a group of mineralized magnetite and lithic breccias within the ca. 2.05- to 1.90-Ga Proterozoic supracrustal sequence of the Kiruna district, northern Sweden. Potentially economic grades of Cu and Au, largely in the form of chalcopyrite and other sulfide assemblages, are hosted in brecciated magnetite and metavolcanic rocks. The extent of the mineralization is currently open, both downdip and along strike. The deposit was discovered through an integrated geophysical and geochemical program focused on iron oxide-copper-gold (IOCG)–style mineralization. It is hosted by brecciated greenschist facies metavolcanic rocks within and adjacent to an east-northeast–trending shear zone. The dominant characteristics of the deposit are consistent with the IOCG class and include magnetite and lithic breccias hosted in a metavolcanic sequence, with matrices of albite, actinolite, and calcite surrounded by halos of sodic (albitescapolite) and potassic (scapolite-K-feldspar-biotite) alteration. A distinctive accessory mineral assemblage includes apatite, titanite, and allanite. The paragenesis and textural evolution of the deposit includes early Narich alteration accompanying massive magnetite alteration. The Na-rich alteration is overprinted by potassic alteration (also associated with magnetite), although the paragenesis is complex and multiple generations of both sodic and potassic alteration are recognized. Alteration of lithic clasts to magnetite confirms a metasomatic origin, as opposed to an orthomagmatic origin, for the magnetite mineralization. Re-Os analyses of two separates of molybdenite intergrown with magnetite, interpreted as cogenetic with the sulfide assemblage, yield mineralization ages of 1853 ± 6 and 1862 ± 6 Ma. Reconnaissance bulk-rock chemistry of the host volcanic rocks is consistent with an intermediate volcanic protolith, but much of the original character of the rocks is masked by albitization and incipient iron, sodic, and potassic alteration. The data also indicate significant element mobility during metasomatism and, in particular, the addition of Ti to the rock mass in biotite and as titanite. The compositions of secondary minerals are consistent with alteration and mineralization caused by highly saline fluids of relatively low F activity. The stable isotope characteristics of calcite, with δ18OSMOW ranging from 9.43 to 19.89 per mil and δ13CPDB ranging from –11.69 to +4.88 per mil, suggest that the fluids of the calcite and sulfide stage were derived from a magmatic source but had interacted extensively with local sedimentary and volcanic rocks.

The past decade has seen renewed interest in 187Re–187Os geochronology using a variety of matrices including sulfide minerals, shales and meteorites. The most widely used value of the 187Re decay constant (λ 187Re) is 1.666 ± 0.005 × 10−11 a−1 (±0.31%), which is based on cross calibration of Re–Os and Pb–Pb chronometers for certain meteorites [Smoliar M. I., Walker R. J., and Morgan J. W. (1996) Re–Os isotope constraints on the age of Group IIA, IIIA, IVA, and IVB iron meteorites. Science 271, 1099–1102]. However, other recent studies have yielded alternate values of λ 187Re, based upon either direct counting experiments or analysis of meteorites. Here, we provide an independent assessment of λ 187Re, using methodology, sample materials, and preparation of Os standard solutions different from those of Smoliar et al. (1996). Combining Re–Os age data for molybdenite formed in magmatic ore deposits, with the U–Pb zircon age of the magmatic rocks, a refined λ 187Re value is determined by averaging 11 individual cross-calibration experiments spanning ca. 2700 Ma of Earth history. Using the U decay constants of Jaffey [Jaffey A. H., Flynn K. F., Glendenin L. E., Bentley W. C., and Essling A. M. (1971) Precision measurement of half-lives and specific activities of 235U and 238U. Phys. Rev. 4, 1889–1906], a value for λ 187Re of 1.6668 ± 0.0034 × 10−11 a−1 is determined. Using the λ 238U value of Jaffey et al. (1971) and λ 235U value of Schoene [Schoene B., Crowley J. L., Condon D. J., Schmitz M. D., and Bowring S. A. (2006) Reassessing the uranium decay constants for geochronology using ID-TIMS U–Pb data. Geochim. Cosmochim. Acta 70, 426–445], a value for λ 187Re of 1.6689 ± 0.0031 × 10−11 a−1 is determined. These values are nominally higher (ca. 0.1 and ca. 0.2%) than the value determined by Smoliar et al. [Smoliar M. I., Walker R. J., and Morgan J. W. (1996) Re–Os isotope constraints on the age of Group IIA, IIIA, IVA, and IVB iron meteorites. Science 271, 1099–1102], but within calculated uncertainty. Further refinement of λ187Re by cross calibrating the molybdenite and U–Pb zircon chronometers should be possible by utilizing high precision, single-grain, chemical abrasion zircon U–Pb analyses.

The Cadia district, located in the eastern Lachlan fold belt of New South Wales, Australia, comprises four gold-copper porphyry deposits (Ridgeway, Cadia Quarry, Cadia Hill, and Cadia East) and two related ironcopper- gold skarn deposits (Big Cadia and Little Cadia). These deposits formed along a northwest-striking, arctransverse structural corridor within the intraoceanic Macquarie arc. This arc is composed of a belt of Early Ordovician to Early Silurian mafic to intermediate volcanic, volcaniclastic, and intrusive rocks of calc-alkalic to alkalic composition. The Cadia porphyry deposits are temporally and genetically associated with composite intrusive complexes of alkalic monzodiorite to quartz monzonite. U-Pb dating of igneous minerals from the intrusions and Re-Os dating of hydrothermal molybdenite from the deposits has revealed the presence of two temporally discrete events of magmatism and related porphyrystyle mineralization in the Cadia district. The monzonitic intrusive complex related to mineralization at Ridgeway and a quartz monzonite porphyry stock that lies immediately southwest of the Cadia Quarry deposit are early Late Ordovician (456-454 Ma). In contrast, the quartz monzonite porphyry stock that hosts the Cadia Quarry and Cadia Hill orebodies and an intermineral quartz monzonite porphyry dike at Cadia East are Early Silurian (~438 Ma). Re-Os molybdenite ages determined for quartz-sulfide veins within the early Late Ordovician quartz monzonite porphyry confirm multiple episodes of mineralization associated with the Cadia Quarry deposit, suggesting a complex history between 460 and 450 Ma. At Cadia Hill, Cadia Quarry, and Cadia East, a widespread event of porphyry gold-copper mineralization is recorded at about 443 to 441 Ma, based on three Re-Os molybdenite ages from sheeted quartz sulfide veins. Similar ages for magmatic zircon from the host intrusions support a link between dated intrusions and mineralization. These new ages are in general agreement with the ages of other porphyry gold-copper and related epithermal deposits of the Eastern Lachlan fold belt and help to constrain the relationship between the Cadia region and the evolution of the Lachlan fold belt. It is notable that the high-grade Ridgeway deposit is up to 18 m.y. older than any alkalic porphyry deposit yet discovered in the Macquarie arc, a feature that may be important for continued exploration success in this region.

Granites and primary tin mineralization in the Erzgebirge were dated using (1) conventional U–Pb dating of uraninite inclusions in mica, (2) Rb–Sr dating of inclusions in quartz that represent highly evolved melts, (3) Re–Os dating of magmatic–hydrothermal molybdenite, and (4) chemical Th–U–Pb dating of uraninite. Conventional isotope dilution and thermal ion mass spectrometry and chemical Th–U–Pb dating of uraninite in granites from the Ehrenfriedersdorf mining district provide ages of 323.9 ± 3.5 Ma (2σ; Greifenstein granite) and 320.6 ± 1.9 and 319.7 ± 3.4 Ma (2σ, both Sauberg mine), in agreement with U–Pb apatite ages of 323.9 ± 2.9 and 317.3 ± 1.6 Ms (2σ, both Sauberg mine). Rb–Sr analysis of melt inclusions from Zinnwald gives highly radiogenic Sr isotopic compositions that, with an assumed initial Sr isotopic composition, permit calculation of precise ages from single inclusions. The scatter of the data indicates that some quartz-hosted melt inclusions have been affected by partial loss of fluid exsolved from the melt inclusion. Re–Os dating of two molybdenite samples from Altenberg provides ages of 323.9 ± 2.5 and 317.9 ± 2.4 Ma (2σ). Together with age data from the literature, our new ages demonstrate that primary tin mineralization and the emplacement of the large Sn-specialized granites in the Erzgebirge fall in a narrow range between 318 and 323 Ma. Primary Sn mineralization occurred within a short interval during post-collisional collapse of the Variscan orogen and was essentially synchronous over the entire Erzgebirge. In contrast to earlier claims, no systematic age difference between granites of the eastern and western Erzgebirge was established. Furthermore, our data do not support a large age range for Late-Variscan granites of the Erzgebirge (330–290 Ma), as has been previously suggested.

The area of the Middle–Lower Yangtze River valley, Eastern China, extending from Wuhan (Hubei province) to western Zhenjiang (Jiangsu province), hosts an important belt of Cu–Au–Mo and Fe deposits. There are two styles of mineralization, i.e., skarn/porphyry/stratabound Cu–Au–Mo–(Fe) deposits and magnetite porphyry deposits in several NNE-trending Cretaceous fault-bound volcanic basins. The origin of both deposit systems is much debated. We dated 11 molybdenite samples from five skarn/porphyry Cu–Au–Mo deposits and 5 molybdenite samples from the Datuanshan stratabound Cu–Au–Mo deposit by ICP-MS Re–Os isotope analysis. Nine samples from the same set were additionally analyzed by NTIMS on Re–Os. Results from the two methods are almost identical. The Re–Os model ages of 16 molybdenite samples range from 134.7 ± 2.3 to 143.7 ± 1.6 Ma (2 σ ). The model ages of the five samples from the Datuanshan stratabound deposit vary from 138.0 ± 3.2 to 140.8 ± 2.0 Ma, with a mean of 139.3 ± 2.6 Ma; their isochron age is 139.1 ± 2.7 Ma with an initial Os ratio of 0.7 ± 8.1 (MSWD = 0.29). These data indicate that the porphyry/skarn systems and the stratabound deposits have the same age and suggest an origin within the same metallogenic system. Albite 40 Ar/ 39 Ar dating of the magnetite porphyry deposits indicates that they formed at 123 to 125 Ma, i.e., 10–20 Ma later. Both mineralization styles characterize transitional geodynamic regimes, i.e., the period around 140 Ma when the main NS-trending compressional regime changed to an EW-trending lithospheric extensional regime, and the period of 125–115 Ma of dramatic EW-trending lithospheric extension.

The Felbertal scheelite deposit in the Eastern Alps has been regarded as the type locality for stratabound scheelite deposits. It is hosted by a Cambro-Ordovician metavolcanic arc sequence with minor Variscan granitoids (∼ 340 Ma) in the central Tauern Window. Re–Os model ages for molybdenite from the Felbertal tungsten deposit range between ∼ 358 and ∼ 336 Ma and record several pulses of magmatic-hydrothermal-metamorphic molybdenite formation. Molybdenite ages from the K2 orebody, a scheelite-rich quartz mylonite in the Western ore field, indicate that both mineralisation and mylonite are Variscan in age and suggest that the shear zone was active for ∼ 20 million years. Early stage tungsten mineralisation (Scheelite 1) in quartzitic ores in the Eastern ore field, which is free of molybdenite, yielded very low to near blank levels of Re and Os and thus could not be dated. However, molybdenite from scheelite–quartz stringers, previously interpreted as a feeder stockwork to quartzitic scheelite ore of presumed Cambrian age, yielded Variscan Re–Os ages of ∼ 342 and ∼ 337 Ma. Dating of molybdenite contained in scheelite ores thus far provides no indication of a Cambrian component to the tungsten mineralisation. Our data are consistent with a model of either granite intrusion-related ore formation and coeval metamorphic overprint during the Early Carboniferous or, alternatively, molybdenite formation may be exclusively attributed to Variscan metamorphism (see Stein 2006).

Re–Os dating of molybdenite is an accurate means to date intrusions and intrusion-related ore deposits using the model age or isochron approach. But, molybdenite has a new niche in the greenschist- to granulite-facies metamorphic environment. Re–Os ages for metamorphic molybdenite may be used to construct regional metamorphic histories. Age significance and accuracy are established by analyzing multiple molybdenite separates extracted from single, petrographically-characterized molybdenite occurrences. In this study, twelve geologically distinct molybdenite-bearing samples from two small Mo districts in northern Sweden trace a 150 m.y. Paleoproterozoic Svecofennian metamorphic history from ∼1900 to 1750 Ma. These data reveal a little-known, widespread and protracted, Late Svecofennian anatexis in northern Sweden. The Kataberget Mo–(Cu, F) deposit is located in the Moskosel granite batholith north of the economically-renown Skellefte district. Four different molybdenite samples from outcrop at Kataberget indicate an intrusion age of 1895 ± 6 Ma with the formation of later pegmatite–aplite at 1875 ± 6 Ma. The Allebuoda (Bjorntjarn) and Munka Mo–(W) deposits in the Rappen district are represented by three outcrop and five drill core samples of molybdenite-bearing aplite–pegmatite–granite. These two deposits were previously described as intrusion-related Climax-type Mo mineralization. Re–Os ages for molybdenites from these deposits range from 1865 to 1750 Ma and, significantly, Re concentrations are markedly low, extending to the sub-ppm level. Age agreement within the deposits is conspicuously lacking, whereas, with one exception, age agreement within any single sample (geologic occurrence), as established by analysis of additional molybdenite separates, is very good. These data, together with fundamental geologic observations discussed in this paper, suggest that Mo–(W) mineralization in northern Sweden is not intrusion-related, but the local product of episodic melting of Archean–Paleoproterozoic supracrustal gneisses related to the Svecofennian orogeny. Petrographic traverses across the boundary between widespread, foliation-parallel units of aplitic to pegmatitic pink granite and hosting biotite gneiss directly capture the process of ore formation. Dehydration breakdown of zircon-rich biotite aligned with the foliation in the gneiss is accompanied by formation of new pristine, post-deformational biotite plus sulfides, oxides, hydrothermal zircon and fluorite, all associated with microcline-dominant leucosomes. This process has profound implication for the traditional leucogranite, intrusion-related genesis attributed to the broad classification of Mo–W–Sn–base and precious metal mineralization (e.g., South Mountain Batholith, Nova Scotia; Okiep, Namaqualand, South Africa; Mactung, Yukon; Pogo–Liese, Tintina, Alaska; Carajas and Goias–Rio Tocantins, Brazil; New England Batholith, NSW, Australia; Bergslagen, Sweden; Nevoria, Western Australia; Alpeinerscharte, Austria; Erzgebirge, Germany; Sardinia–Corsica Batholith). In addition to biotite, metallogenic contributions (e.g., Mo, W, Sn, U, Bi, Cu, Pb, Zn, Fe, Ni, Co, Au, Ag, Te, As, Sb, REE) in various combinations may also be controlled by breakdown of amphibole. In effect, the trace element composition of dehydrating or recrystallizing components in a gneissic rock essentially defines the local and district metallogenic suite. In the absence of focusing structures (e.g., shear zones, sheeted vein development), this process will generally form small and disconnected subeconomic deposits with erratic and unpredictable grades. Low Re content in associated molybdenite is a key indicator for a subeconomic origin by local melting of biotite gneiss (Mo–W) or muscovite schist (Sn–W).

Re–Os dating of molybdenite from small deposits is used to define crustal domains exhibiting ductile versus brittle behaviour during gravitational collapse of the Sveconorwegian orogen in SW Scandinavia. A 1019 ± 3 Ma planar quartz vein defines a minimum age for brittle behaviour in central Telemark. In Rogaland–Vest Agder, molybdenite associated with deformed quartz and pegmatite veins formed between 982 ± 3 and 947 ± 3 Ma in the amphibolite-facies domain (three deposits) and between 953 ± 3 and 931 ± 3 Ma west of the clinopyroxene-in isograd (two deposits) in the vicinity of the 0.93–0.92 Ga Rogaland anorthosite complex. The data constrain the last increment of ductile deformation to be younger than 0.95 and 0.93 Ga in these two metamorphic zones, respectively. Molybdenite is the product of an equilibrium between biotite, oxide and sulfide minerals and a fluid or hydrated melt phase, after the peak of 1.03–0.97 Ga regional metamorphism. Molybdenite precipitation is locally episodic. A model for gravitational collapse of the Sveconorwegian orogen controlled by lithospheric extension after 0.97 Ga is proposed. In the west of the orogen, the Rogaland–Vest Agder sector is interpreted as a large shallow gneiss dome, formed slowly in two stages in a warm and structurally weak crust. The first stage at 0.96–0.93 Ga was associated with intrusion of the post-collisional hornblende–biotite granite suite. The second stage at 0.93–0.92 Ga, restricted to the southwesternmost area, was associated with intrusion of the anorthosite–mangerite–charnockite suite. Most of the central part of the orogen was already situated in the brittle upper crust well before 0.97 Ga, and did not undergo significant exhumation during collapse. In the east of the orogen, situated against the colder cratonic foreland, exhumation of high-grade rocks of the Eastern Segment occurred between 0.97 and 0.95 Ga, and included preservation of high-pressure rocks but no plutonism.