Sulfur cycling at the Mid-Atlantic Ridge: A multiple sulfur isotope approach

The role of sulfur in two hydrothermal vent systems, the Logatchev hydrothermal field at 14°45′N/44°58′W and several different vent sites along the southern Mid-Atlantic Ridge (SMAR) between 4°48′S and 9°33′S and between 12°22′W and 13°12′W, is examined by utilizing multiple sulfur isotope and sulfur concentration data. Isotope compositions for sulfide minerals and vent H₂S from different SMAR sites range from + 1.5 to + 8.9‰ in δ³⁴S and from + 0.001 to + 0.051‰ in Δ³³S. These data indicate mixing of mantle sulfur with sulfur from seawater sulfate. Combined δ³⁴S and Δ³³S systematics reveal that vent sulfide from SMAR is characterized by a sulfur contribution from seawater sulfate between 25 and 33%. This higher contribution, compared with EPR sulfide, indicates increased seawater sulfate reduction at MAR, because of a deeper seated magma chamber and longer fluid upflow path length, and points to fundamental differences with respect to subsurface structures and fluid evolution at slow and fast spreading mid-ocean ridges.Additionally, isotope data uncover non-equilibrium isotopic exchange between dissolved sulfide and sulfate in an anhydrite bearing zone below the vent systems at fluid temperatures between 335 and 400 °C. δ³⁴S values between + 0.2 to + 8.8‰ for dissolved and precipitated sulfide from Logatchev point to the same mixing process between mantle sulfur and sulfur from seawater sulfate as at SMAR. δ³⁴S values between ? 24.5 and + 6.5‰ and Δ³³S values between + 0.001 and + 0.125‰ for sulfide-bearing sediments and mafic/ultramafic host rocks from drill cores taken in the region of Logatchev indicate a clear contribution of biogenic sulfides formed via bacterial sulfate reduction. Basalts and basaltic glass from SMAR sites with Δ³³S = ? 0.008‰ reveal lower Δ³³S lower values than suggested on the basis of previously published isotopic measurements of terrestrial materials.We conclude that the combined use of both δ³⁴S and Δ³³S provides a more detailed picture of the sulfur cycling in hydrothermal systems at the Mid-Atlantic Ridge and uncovers systematic differences to hydrothermal sites at different mid-ocean ridge sites. Multiple sulfur isotope measurements allow identification of incomplete isotope exchange in addition to isotope mixing as a second important factor influencing the isotopic composition of dissolved sulfide during fluid upflow. Furthermore, based on Δ³³S we are able to clearly distinguish biogenic from hydrothermal sulfides in sediments even when δ³⁴S were identical.     

Sulfur and lead isotopic compositions of massive sulfides from deep-sea hydrothermal systems: Implications for ore genesis and fluid circulation

Studies of sulfur and lead isotopic compositions in hydrothermal deposits are an important tool to determine the source and processes of both sulfur and lead, and to understand the origin of hydrothermal ore deposits. Here, the sulfur and lead isotopic compositions of sulfide minerals have been studied for different hydrothermal fields in the East Pacific Rise (EPR), Mid-Atlantic Ridge (MAR), Central Indian Ridge (CIR), Southwest Indian Ridge (SWIR), and North Fiji Basin (NFB). The sulfur isotopic compositions of the studied sulfide samples are variable (δ³⁴S 0.0 to 9.6‰, avg. δ³⁴S 4.7‰; n = 60), being close to the associated igneous rocks (~ 0‰ for, e.g., basalt, serpentinized peridotite), which may reflect the S in the sulfide samples is derived mainly from the associated igneous rocks, and a relatively small proportion (< 36%) of seawater sulfur incorporated into these sulfides during mixing between seawater (δ³⁴S 21‰) and hydrothermal fluid. In contrast for a mixed origin for the source of S, the majority of the lead isotopic compositions (²⁰⁶Pb/²⁰⁴Pb 17.541 ± 0.004 to 19.268 ± 0.001, ²⁰⁷Pb/²⁰⁴Pb 15.451 ± 0.001 to 15.684 ± 0.001, ²⁰⁸Pb/²⁰⁴Pb 37.557 ± 0.008 to 38.988 ± 0.002, n = 21) of the sulfides possess a basaltic Pb isotopic composition, suggesting that the lead in the massive sulfide is mainly leached from local basaltic rocks that host the sub-seafloor hydrothermal systems in sediment-free mid-ocean ridges and mature back-arc basins. Furthermore, sulfide minerals in the super-fast and fast spreading mid-ocean ridges (MORs) exhibit less spread in their the δ³⁴S values compared to sulfides from super-slow, and slow spreading MORs, which is most easily explained as a lesser degree of fluid-rock interaction and hydrothermal fluid-seawater mixing during hydrothermal ore-forming process. Additionally, the S and Pb isotope compositions of sulfides are controlled by the fluid processes for forming seafloor massive sulfide deposits. We demonstrate that the variable sulfur and lead isotopic compositions exhibit a relationship with the sulfur and lead sources, fluid–rock interaction, and fluid–seawater mixing.     

Dependence of mid-ocean ridge morphology on spreading rate in numerical 3-D models

The morphology of natural mid-ocean ridges changes significantly with the rate of extension. Full spreading rate on Earth varies over more than one order of magnitude, ranging from less than 10 mm/yr at the Gakkel Ridge in the Arctic Ocean to 170 mm/yr at the East Pacific Rise. The goal of this study is to reproduce and investigate the spreading patterns as they vary with extension rate using 3-D thermomechanical numerical models. The applied finite difference marker-in-cell code incorporates visco-plastic rheology of the lithosphere and a crustal growth algorithm. The evolution of mid-ocean ridges from nucleation to a steady-state is modelled for a wide range of spreading rates. With increasing spreading rate, four different regimes are obtained: (a) stable alternating magmatic and amagmatic sections (≈ 10 mm/yr), (b) transient features in asymmetrically spreading systems (≈ 20 mm/yr), (c) stable orthogonal ridge-transform fault patterns (≈ 40 mm/yr) and (d) stable curved ridges (≥ 60 mm/yr). Modelled ultraslow and slow mid-ocean ridges share key features with natural systems. Abyssal hills and oceanic core complexes are the dominant features on the flanks of natural slow-spreading ridges. Numerically, very similar features are produced, both generated by localised asymmetric plate growth controlled by a spontaneous development of large-offset normal faults (detachment faults). Asymmetric accretion in our models implies a lateral migration of the ridge segment, which might help explaining the very large offsets observed at certain transform faults in nature.     

Geochemical signature and rock associations of ocean ridge-subduction: Evidence from the Karamaili Paleo-Asian ophiolite in east Junggar,NW China

Subduction of active spreading ridges most likely occurs throughout Earth's history. Interaction or collision between spreading center and trench, with the active spreading ridge downgoing and shallowly being buried in subduction zone, results in low-pressure but high-temperature near-trench magmatism in the forearc and accretionary prism setting. The Central Asian region, a complex orogenic belt created during the evolution and closure of the Paleo-Asian Ocean (PAO) at ~ 1000–300 Ma, provides an ideal place to study the subduction of PAO spreading ridges beneath ancient continental margins. It had been suggested that the low-pressure and high-temperature mafic and intermediate to felsic magmas from the Karamaili ophiolite (KO) in the NE corner of the Junggar basin (NW China) in Central Asia were likely produced by ridge subduction (Liu et al., 2007). In this paper, we combine our new geochemical data with previous results to show that the geochemical characteristics of the bulk of KO mafic rocks range from arc basalt-like to mid-ocean ridge basalt-like and ocean island basalt-like. Their trace element patterns range from depleted to enriched in highly incompatible elements, but depleted in Nb and Ta, indicating a subduction-influenced origin. The KO intermediate to felsic rocks are calc-alkaline and boninitic in composition and have trace element signatures similar to the associated mafic rocks. The low Nb/Ta ratios of some of the mafic rocks and boninitic character of some of the intermediate to felsic rocks reflect a highly depleted source, perhaps due to prior backarc magmatism. Major and trace element models indicate complex fractional crystallization histories of parental KO magmas to generate both the mafic and intermediate to felsic rocks, but in general, crystal fractionation occurred at 1000 to 1200 °C and moderate to low (0.5 kbar to 10 kbar) pressure or < 23 km depth. We conclude that the KO was formed in a forearc region of a subduction system that experienced ridge subduction.     

Widespread tectonic extension at the Central Indian Ridge between 8°S and 18°S

The middle part of the Central Indian Ridge (MCIR) between 8°S and 18°S is representative of mid-ocean ridges in the Indian Ocean but has not previously been systematically surveyed. Here we present results from the first high-resolution mapping survey over both on- and off-axis sections of the MCIR including multibeam bathymetry, magnetics, hydrocasting, and seabed sampling. The 700-km-long MCIR consists of six first-order segments that are offset by > 30 km along well-developed transform faults. Three of the first-order segments are further divided into seven second-order segments with < 30 km offset along non-transform discontinuities. We have recognized for the first time 11 prominent ocean core complexes (OCCs). These occur at nearly all segment ends, corresponding to an occurrence every 60 km of the surveyed ridge. Seafloor spreading model studies using magnetic reversals show that the MCIR is a slow-spreading ridge with average full opening rates ranging from 33.7 to 45.1 mm/yr, increasing from north to south. The highly curved and intermittent axial ridge geometry, rugged flank fabric, variation in the depth and width of the middle valley, and the frequent occurrences of ocean core complexes and non-transform discontinuities demonstrate that asymmetric accretionary processes are dominant along the ridge. The spreading rate symmetry combined with morphotectonic features, reveal that the MCIR segments developed mainly via tectonic extension with little magmatism. Segments with asymmetric accretion controlled by tectonic extension makes up ~ 96% of the MCIR, whereas symmetric accretion controlled by robust magmatism make up < 4%. Hydrothermal plumes with high methane concentrations occur frequently over the OCCs. This finding indicates that abundant OCCs exposed by detachment faults lead to extensive hydrothermal circulation at off-axis areas and that detachment faults are the primary fluid path for hydrothermal fluid circulation at off-axis regions. Serpentinization of mantle-derived rock at OCCs may be one of the major sources of heat and methane in off-axis areas.     

Internal architecture of a raised beach ridge system (Anholt,Denmark) resolved by ground-penetrating radar investigations

The internal architecture of raised beach ridge and associated swale deposits on Anholt records an ancient sea level. The Holocene beach ridges form part of a progradational beach ridge plain, which has been interpreted to have formed during an isostatic uplift and a relative fall in the sea level over the past 7700 years. The ridges are covered by pebbles and cobbles and commonly show evidence of deflation. Material presumably removed from the beach ridges and adjacent swales form the present dune forms on Anholt. Ground-penetrating radar (GPR) reflection lines have been collected with 250 MHz shielded antennae across the fossil ridge and swale structures. The signals penetrate the subsurface to a maximum depth of ～ 10 m below the fossil features. The GPR data resolve the internal architecture of the beach ridges and swales with a vertical resolution of about 0.1 m. GPR mapping indicates that the Holocene beach ridges are composed of seaward-dipping beachface deposits as well as minor amounts of inland dipping deposits of wash-over origin. The beachface deposits downlap on underlying shoreface deposits, and we use these surfaces as markers of a relative palaeo-sea level. The new data indicate that the highest relative sea level at about 8.5 m was reached 6500 years ago; 700 years later the relative sea level had dropped 0.7 m indicating a change in the relative sea level around 1 mm/year. This fall in the relative sea level most likely records the influence of an isostatic rebound causing younger beach ridge deposits to indicate lower sea levels.     

Massive sulfides of Mount Jourdanne along the super-slow spreading Southwest Indian Ridge and their genesis

Modern massive sulfide deposits are known to occur in diverse tectonic settings and it is generally expected that hydrothermal deposits of similar geological settings shall have more or less similar mineralogical and geochemical signatures. However, the Mount Jourdanne sulfide deposits along the super-slow spreading Southwest Indian Ridge deviate from this common concept. These sulfide precipitates are Zn-rich (up to 35 wt.%) and are characterized by high concentrations of Pb (≤ 3.5 wt.%), As (≤ 1.1 wt.%), Ag (≤ 0.12 wt.%), Au (≤ 11 ppm), Sb (≤ 967 ppm), and Cd (≤ 0.2 wt.%) which are unusual for a modern sediment-free mid-oceanic ridge system. Therefore, we have reinvestigated the sulfide samples collected during the INDOYO cruise in 1998, in order to explain their unusual mineralogy and geochemical composition. The sulfide samples are polymetallic and are classified as: a) chimneys, b) mounds, and c) hydrothermal breccias. The chimneys are small tube-like symmetrical bodies (30–40 cm high; ~ 10 cm diameter) and consist mainly of sphalerite and less chalcopyrite, set in a matrix of late amorphous silica. The inner wall shows a late-stage colloform sphalerite containing co-precipitates of galena and/or Pb–As sulfosalts. In contrast, the mound samples are dominated either by Fe-sulfides (pyrite) or by a mixture of pyrite and chalcopyrite with less sphalerite, pyrrhotite, amorphous silica and barite. Both, the chimney and mound samples, are characterized by layering and mineral zonation. The hydrothermal breccias are highly altered and mineralogically heterogeneous. They consist of silicified basaltic material that are impregnated with sulfides and contain cm-sized chimney fragments within a matrix of low-temperature minerals such as sphalerite and pyrite. The latter fragments mainly consist of chalcopyrite with isocubanite lamellae. In addition, these breccias contain late-stage realgar, boulangerite, galena, Pb–As sulfosalts and barite that are mostly confined to vugs or fractures. At least five mineralogical associations are distinguished that indicate different thermal episodes ranging from black smoker mineralization conditions to cessation of the hydrothermal activity. Based on the mineralogical associations and established literature in this regard, it is inferred that the mineralization at Mt. Jourdanne occurred mainly in three temperature domains. Above 300 °C, the chalcopyrite (with isocubanite)–pyrrhotite association formed whereas the sphalerite dominated assemblage with much less chalcopyrite and pyrite formed around and below 300 °C. The late-stage mineralization (below 200 °C) contains colloform sphalerite, galena, Pb–As sulfosalts, realgar and barite. The unusual mineralogy and trace element chemistry for this modern VHMS deposit could be explained assuming hydrothermal leaching of some felsic differentiates underneath the basaltic cover and subsequent zone refining processes.     

Cu–(Ni–Co–Au)-bearing massive sulfide deposits associated with mafic–ultramafic rocks of the Main Urals Fault,South Urals: Geological structures,ore textural and mineralogical features,comparison with modern analogs

Cu-rich massive sulfide deposits associated with mafic–ultramafic rocks in the southern portion of the Main Urals Fault (MUF) are characterized by variable enrichments in Ni (up to 0.45 wt.%), Co (up to 10 wt.%) and Au (up to 16 ppm in individual hand-specimens). The Cu (Ni–Co)-rich composition of MUF deposits, as opposed to the Cu (Zn)-rich composition of more eastward massive sulfide deposits of broadly similar age along the western flank of the Magnitogorsk arc, reflects the abundance of seafloor-exposed, Ni–Co-rich ultramafic rocks in the most external portion of the Early-Devonian Magnitogorsk forearc. Morphological, textural, and compositional differences between individual deposits are interpreted to be the result of the sulfide deposition style and, in part, of the original subseafloor lithology. One deposit produced by dominantly on-seafloor hydrothermal processes is characterized by pyrite–marcasite ≫ pyrrhotite, not so low Zn grades (occasionally up to 2 wt.%), abundant clastic facies and periodical superficial oxidation. Deposits produced by dominantly subseafloor hydrothermal processes are characterized by pyrrhotite > pyrite, very low Zn (generally < to ≪ 0.1 wt.%), volumetrically minor clastic facies, and multi-layer deposit morphology. Very low Ni/Co ratios in the on-seafloor deposit may indicate a dominant metal contribution from a mafic rather than ultramafic source. The sulfide mineralization was associated with extensive hydrothermal alteration of the host ultramafic and mafic rocks, leading to formation of abundant talc, talc–carbonate and chlorite rocks. Occurrence of large volumes of such altered lithotypes in ophiolitic belts may be considered as a potential searching criteria for MUF-type (Cu, Co, Ni)-deposits. In spite of the contrasting geodynamic environment, geological, geochemical, textural and mineralogical peculiarities of the MUF deposits in many respects are similar to those of ultramafic-hosted massive sulfide deposits along the Mid-Atlantic Ridge. In geological time, supra subduction-zone settings appear to have been more effective than mid-ocean ridge settings for preservation of ultramafic-hosted massive sulfide deposits.     

Origin of glacial ridges (OIS 6) in the Kaskaskia Sublobe,southwestern Illinois,USA

The origin of Illinois Episode (OIS 6) glacial ridges (formerly: ‘Ridged Drift’) in the Kaskaskia Basin of southwestern Illinois is controversial despite a century of research. Two studied ridges, containing mostly fluvial sand (OSL ages: ~ 150 ± 19 ka), with associated debris flows and high-angle reverse faults, are interpreted as ice-walled channels. A third studied ridge, containing mostly fine-grained till, is arcuate and morainal. The spatial arrangement of various ridge types can be explained by a glacial sublobe in the Kaskaskia Basin, with mainly fine-grained ridges along the sublobe margins and coarse-grained glaciofluvial ridges in a paleodrainage network within the sublobe interior. Illinois Episode till fabric and striation data demonstrate southwesterly ice flow that may diverge near the sublobe terminus. The sublobe likely formed as glacial ice thinned and receded from its maximum extent. The Kaskaskia Basin contains some of the best-preserved Illinois Episode constructional glacial landforms in the North American midcontinent. Such distinctive features probably result from ice flow and sedimentation into this former lowland, in addition to minimal postglacial erosion. Other similar OIS 6 glacial landforms may exist in association with previously unrecognized sublobes in the midcontinent, where paleo-lowlands might also have focused glacial sedimentation.     

Geology,U-Pb geochronology,and stable isotope geochemistry of the Tunca semi-massive sulfide mineralization,Black Sea region,NE Turkey: Implications for ore genesis

Upper Cretaceous volcano-sedimentary sequences of the Eastern Pontide orogenic belt, NE Turkey, are host to significant VMS mineralization, including near Tunca. The initial stages of felsic volcanism within the mineralized area are marked by the eruption of dacitic lavas and breccias of the Kızılkaya Formation. This was accompanied by the emplacement of domelike hematitic dacites. Autobrecciated and volcaniclastic rocks, both in situ and resedimented, were likely generated from extrusive portions of these dacite bodies. Basaltic volcanism is marked by the eruption of the lava flows and pillow lavas of the Çağlayan Formation. Hiatuses in basaltic activity are marked by thin horizons of volcaniclastics and mudstones. The uppermost felsic volcanic units were accompanied by resedimentation of autoclastic facies from previous volcanism and represent the latest phase of Upper Cretaceous volcanism in the area. The semi-massive sulfide mineralization is associated with a late stage of the initial felsic volcanism. U-Pb LA-ICP-MS zircon dating of a dacitic tuff breccia yielded an age of 88.1 ± 1.2 Ma (Coniacian-Upper Cretaceous), which is interpreted to be the age of the sulfide occurrences.A concentric zoned alteration pattern is observed in the footwall rocks. The alteration pattern is considered to have formed by lateral migration of hydrothermal fluids which had ascended along the discharge conduit. Fluid inclusion data indicate precipitation or mobilization processes within a relatively narrow temperature range of 152–255 °C (avg. 200 °C). The low-salinity fluids in the fluid inclusions, less than 5.9 wt% NaCl equivalent, are consistent with typical modified seawater-dominant hydrothermal vent fluids. Sulfur isotope analysis of the Tunca sulfides yields a narrow range of 1.5–4.1 per mil. These δ³⁴S values are also typical of many VMS deposits. Most of the recorded δ¹⁸O values (+7.1 to +14.0 per mil) are greater than 9 per mil. The most intensely hydrothermally altered rocks tend to have lower δ¹⁸O values relative to the less altered rocks. Collectively, the geologic relationships, mineralization style, and the lack of seafloor ore facies suggest that mineralization is principally of sub-seafloor origin. The most geologically reasonable interpretation of the genesis of the Tunca mineralization is the continuous interaction between the host rocks and seawater-derived fluids, without significant involvement of a magmatic fluid.     

Dating the giant Zhuxi W–Cu deposit (Taqian–Fuchun Ore Belt) in South China using molybdenite Re–Os and muscovite Ar–Ar system

The recently discovered Zhuxi W–Cu ore deposit is located within the Taqian–Fuchun Ore Belt in the southeastern edge of the Yangtze Block, South China. Its inferred tungsten resources, based on new exploration data, are more than 280 Mt by 2016. At least three paragenetic stages of skarn formation and ore deposition have been recognized: prograde skarn stage; retrograde stage; and hydrothermal sulfide stage. Secondly, greisenization, marmorization and hornfels formation are also observed. Scheelite and chalcopyrite are the dominant metal minerals in the Zhuxi deposit and their formation was associated with the emplacement of granite stocks and porphyry dykes intruded into the surrounding Carboniferous carbonate sediments (Huanglong and Chuanshan formations) and the Neoproterozoic slate and phyllites. The scheelite was mostly precipitated during the retrograde stage, whereas the chalcopyrite was widely precipitated during the hydrothermal sulfide stage. A muscovite ⁴⁰Ar/³⁹Ar plateau age of about 150 Ma is interpreted as the time of tungsten mineralization and molybdenite Re–Os model ages ranging from 145.9 ± 2.0 Ma to 148.7 ± 2.2 Ma (for the subsequent hydrothermal sulfide stage of activity) as the time of the copper mineralization. Our new molybdenite Re–Os and muscovite ⁴⁰Ar/³⁹Ar dating results, along with previous zircon U–Pb age data, indicate that the hydrothermal activity from the retrograde stage to the last hydrothermal sulfide stage lasted up to 5 Myr, from 150.6 ± 1.5 to 145.9 ± 1 Ma, and is approximately coeval or slightly later than the emplacement of the associated granite porphyry and biotite granite. The new ages reported here confirm that the Zhuxi tungsten deposit represents one of the Mesozoic magmatic–hydrothermal mineralization events that took place in South China in a setting of lithospheric extension during the Late Jurassic (160–150 Ma). It is suggested that mantle material played a role in producing the Zhuxi W–Cu mineralization and associated magmatism.     

Seawater contribution to polymetallic Ni–Mo–PGE–Au mineralization in Early Cambrian black shales of South China: Evidence from Mo isotope,PGE, trace element,and REE geochemistry

The Early Cambrian black shale sequence of the Niutitang Formation in South China hosts a synsedimentary, organic carbon-rich, polymetallic sulfide layer with extreme metal concentrations, locally mined as polymetallic Ni–Mo–PGE–Au ore. In combination with previously reported data, we present Mo isotope, platinum-group element (PGE), and trace and rare-earth element (REE) data for the polymetallic sulfide ores and host black shales from four mine sites (Dazhuliushui and Maluhe in Guizhou Province, and Sancha and Cili in Hunan Province, respectively), several hundred kilometers apart. The polymetallic sulfide ores have consistently heavy δ^98/95Mo values of 0.94 to 1.38‰ (avg. 1.13 ± 0.14‰, 1σ, n = 11), and the host black shale and phosphorite have slightly more variable δ^98/95Mo values of 0.81‰ to 1.70‰ (n = 14). This latter variation is due to variable paleoenvironmental conditions from suboxic to euxinic, and partly closed-system fractionation in isolated marine sedimentary basins. Both the polymetallic sulfides and host black shales show PGE distribution patterns similar to that of present-day seawater, but different from those of ancient submarine-hydrothermal deposits and modern submarine hydrothermal fluids. The polymetallic sulfide bed has a generally consistent metal enrichment by a factor of 10⁷ compared to present-day seawater. PAAS-normalized REE + Y patterns of the polymetallic sulfide bed are characterized by a remarkably positive Y anomaly, consistent with an origin of the REE predominantly from seawater. Small positive Eu anomalies in some of the sulfide ores could reflect minor hydrothermal components involved. The Mo isotope, PGE, and trace and rare-earth element geochemical data suggest that metals in the polymetallic Ni–Mo–PGE–Au sulfide ore layer were scavenged mostly from Early Cambrian seawater, by both in-situ precipitation and local re-deposition of sulfide clasts.     

Nickel sulfide deposits in Australia: Characteristics,resources, and potential

Australia's nickel sulfide industry has had a fluctuating history since the discovery in 1966 of massive sulfides at Kambalda in the Eastern Goldfields of Western Australia. Periods of buoyant nickel prices and high demand, speculative exploration, and frenetic investment (the ‘nickel boom’ years) have been interspersed by protracted periods of relatively depressed metal prices, exploration inactivity, and low discovery rates. Despite this unpredictable evolution, the industry has had a significant impact on the world nickel scene with Australia having a global resource of nickel metal from sulfide ores of ∼ 12.9 Mt, five world-class deposits (> 1 Mt contained Ni), and a production status of number three after Russia and Canada. More than 90% of the nation's known global resources of nickel metal from sulfide sources were discovered during the relative short period of 1966 to 1973. Australia's nickel sulfide deposits are associated with ultramafic and/or mafic igneous rocks in three major geotectonic settings: (1) Archean komatiites emplaced in rift zones of granite–greenstone belts; (2) Precambrian tholeiitic mafic–ultramafic intrusions emplaced in rift zones of Archean cratons and Proterozoic orogens; and (3) hydrothermal-remobilized deposits of various ages and settings. The komatiitic association is economically by far the most important, accounting for more than 95% of the nation's identified nickel sulfide resources. The ages of Australian komatiitic- and tholeiitic-hosted deposits generally correlate with three major global-scale nickel-metallogenic events at ∼ 3000 Ma, ∼ 2700 Ma, and ∼ 1900 Ma. These events are interpreted to correspond to periods of juvenile crustal growth and the development of large volumes of primitive komatiitic and tholeiitic magmas caused by large-scale mantle overturn and mantle plume activities. There is considerable potential for the further discovery of komatiite-hosted deposits in Archean granite–greenstone terranes including both large, and smaller high-grade (5 to 9% Ni) deposits, that may be enriched in PGEs (2 to 5 g/t), especially where the host ultramafic sequences are poorly exposed.Analysis of the major komatiite provinces of the world reveals that fertile komatiitic sequences are generally of late Archean (∼ 2700 Ma) or Paleoproterozoic (∼ 1900 Ma) age, have dominantly Al-undepleted (Al₂O₃/TiO₂ = 15 to 25) chemical affinities, and often occur with sulfur-bearing country rocks in dynamic high-magma-flux environments, such as compound sheet flows with internal pathways facies (Kambalda-type) or dunitic compound sheet flow facies (Mt Keith-type). Most Precambrian provinces in Australia, particularly the Proterozoic orogenic belts, contain an abundance of sulfur-saturated tholeiitic mafic ± ultramafic intrusions that have not been fully investigated for their potential to host basal Ni–Cu sulfides (Voisey's Bay-type mineralization). The major exploration challenges for finding these deposits are to determine the pre-deformational geometries and younging directions of the intrusions, and to locate structural depressions in the basal contacts and feeder conduits under cover. Stratabound PGE–Ni–Cu ± Cr deposits hosted by large Archean–Proterozoic layered mafic–ultramafic intrusions (Munni Munni, Panton) of tholeiitic affinity have comparable global nickel resources to many komatiite deposits, but low-grades (< 0.2% Ni). There are also hydrothermal nickel sulfide deposits, including the unusual Avebury deposit in western Tasmania, and some potential for ‘Noril'sk-type’ Ni–Cu–PGE deposits associated with major flood basaltic provinces in western and northern Australia.     

Actively forming Kuroko-type volcanic-hosted massive sulfide (VHMS) mineralization at Iheya North,Okinawa Trough,Japan

Modern seafloor hydrothermal systems provide important insights into the formation and discovery of ancient volcanic-hosted massive sulfide (VHMS) deposits. In 2010, Integrated Ocean Drilling Program (IODP) Expedition 331 drilled five sites in the Iheya North hydrothermal field in the middle Okinawa Trough back-arc basin, Japan. Hydrothermal alteration and sulfide mineralization is hosted in a geologically complex, mixed sequence of coarse pumiceous volcaniclastic and fine hemipelagic sediments, overlying a dacitic to rhyolitic volcanic substrate. At site C0016, located adjacent to the foot of the actively venting North Big Chimney massive sulfide mound, massive sphalerite-(pyrite-chalcopyrite ± galena)-rich sulfides were intersected (to 30.2% Zn, 12.3% Pb, 2.68% Cu, 33.1 ppm Ag and 0.07 ppm Au) that strongly resemble the black ore of the Miocene-age Kuroko deposits of Japan. Sulfide mineralization shows clear evidence of formation through a combination of surface detrital and subsurface chemical processes, with at least some sphalerite precipitating into void space in the rock. Volcanic rocks beneath massive sulfides exhibit quartz-muscovite/illite and quartz-Mg-chlorite alteration reminiscent of VHMS proximal footwall alteration associated with Kuroko-type deposits, characterized by increasing MgO, Fe/Zn and Cu/Zn with depth. Recovered felsic footwall rocks are of FII to FIII affinity with well-developed negative Eu anomalies, consistent with VHMS-hosting felsic rocks in Phanerozoic ensialic arc/back-arc settings worldwide.Site C0013, ∼100 m east of North Big Chimney, represents a likely location of recent high temperature discharge, preserved as surficial coarse-grained sulfidic sediments (43.2% Zn, 4.4% Pb, 5.4% Cu, 42 ppm Ag and 0.02 ppm Au) containing high concentrations of As, Cd, Mo, Sb, and W. Near surface hydrothermal alteration is dominated by kaolinite and muscovite with locally abundant native sulfur, indicative of acidic hydrothermal fluids. Alteration grades to Mg-chlorite dominated assemblages at depths of >5 mbsf (metres below sea floor). Late coarse-grained anhydrite veining overprints earlier alteration and is interpreted to have precipitated from down welling seawater as hydrothermal activity waned. At site C0014, ∼350 m farther east, hydrothermal assemblages are characterized by illite/montmorillonite, with Mg-chlorite present at depths below ∼30 mbsf. Recovered lithologies from distal, recharge site C0017 are unaltered, with low MgO, Fe₂O₃ and base metal concentrations.Mineralization and alteration assemblages are consistent with the Iheya North system representing a modern analogue for Kuroko-type VHMS mineralization. Fluid flow is focussed laterally along pumiceous volcaniclastic strata (compartmentalized between impermeable hemipelagic sediments), and vertically along faults. The abundance of Fe-poor sphalerite and Mg-rich chlorite (clinochlore/penninite) is consistent with the lower Fe budget, temperature and higher oxidation state of felsic volcanic-hosted hydrothermal systems worldwide compared to Mid Ocean Ridge black smoker systems.     

Hydrothermalism in the Tyrrhenian Sea: Inorganic and microbial sulfur cycling as revealed by geochemical and multiple sulfur isotope data

The Palinuro volcanic complex and the Panarea hydrothermal field, both located in the Tyrrhenian Sea (Italy), are associated with island arc magmatism and characterized by polymetallic sulfide mineralization. Dissolved sulfide concentrations, pH, and Eh measured in porewaters at both sites reveal a variable hydrothermal influence on porewater chemistry.Multiple sulfur isotopic measurements for disseminated sulfides (CRS: chromium reducible sulfur) extracted from sediments at Palinuro yielded a broad range in δ³⁴S range between ?29.8 and + 10.2‰ and Δ³³S values between + 0.015 and + 0.134‰. In contrast, sediments at Panarea exhibit a much smaller range in δ³⁴S_CRS with less negative values between ?11.3 and ?1.8‰. The sulfur isotope signatures are interpreted to reflect a mixture between hydrothermal and biogenic sulfide, with a more substantial biogenic contribution at Panarea.Multiple sulfur isotope measurements were performed on sulfides and elemental sulfur from drill core material from the Palinuro massive sulfide complex. δ³⁴S and Δ³³S values for pyrite between ?32.8 and ?1.1‰ and between ?0.012 to + 0.042‰, respectively, as well as for elemental sulfur with δ³⁴S and Δ³³S values between ?26.7 and ?2.1‰ and between + 0.035 and + 0.109‰, respectively, point to a microbial origin for much of the sulfide and elemental sulfur studied. Moreover, data suggest a coupling of bacterial sulfate reduction, sulfide oxidation and sulfur disproportionation. In addition, δ³⁴S values for barite between + 25.0 and + 63.6‰ are also in agreement with high microbial turnover of sulfate at Palinuro.Although a magmatic SO₂ contribution towards the formation of the Palinuro massive sulfide complex is very likely, the activity of different sulfur utilizing microorganisms played a fundamental role during its formation. Thus, porewater and multiple sulfur isotope data reveal differences in the hydrothermal activity at Palinuro and Panarea drill sites and underline the importance of microbial communities for the origin of massive sulfide mineralizations in the hydrothermal subsurface.     

Occurrences and distribution of “invisible” precious metals in sulfide deposits from the Edmond hydrothermal field,Central Indian Ridge

Here, we report the first documented occurrences of “invisible” gold and silver in seafloor sulfide deposits from an active hydrothermal system on the Central Indian Ridge. A detailed mineralogical and geochemical study of polymetallic sulfides from the Edmond vent field was conducted in order to identify controls on the distribution of precious metals. Bulk samples (N = 18) contain up to 18.7 ppm Au and 1450 ppm Ag, with average concentrations of 2.3 ppm Au and 218.9 ppm Ag. Among them, several Zn-rich chimney fragments and anhydrite-dominated ore samples have higher contents of precious metals than Fe-Cu-rich massive sulfides and silica-rich hydrothermal precipitates. Native gold grains are mainly associated with sphalerite, anhydrite, barite and Fe-oxyhydroxides. Abundant submicroscopic Au-Ag alloys tend to occur along grain boundaries between Cu-Fe sulfides and tennantite, or close to the rims of Fe-poor sphalerite. In contrast to primary electrum with high Ag/Au ratios, the absence of detectable silver in high-purity gold indicates that secondary Au enrichment has probably occurred after a direct co-precipitation with Zn-rich mineral assemblages upon cooling and mixing of vent fluids with cold seawater. A suite of late-stage Ag-rich phases, including argentotennantite, pearceite and acanthite, occur as crack-filling veinlets and patches in low-temperature fahlores, or as tiny inclusions enclosed by pyrite, chalcopyrite and colloform sphalerite. By using HRTEM combined with HAADF-STEM imaging, we have found out that silver is also present in significant quantities as discrete colloidal nanoparticles in tennantite. Minor native copper is closely associated with altered chalcopyrite, sphalerite and covellite, exhibiting signs of dissolution, recrystallization and reprecipitation. Extensive hydrothermal reworking resulted from a long history of high-temperature venting in this field, together with post-depositional supergene replacement processes (involving oxidation, leaching or coupled dissolution-reprecipitation mechanisms facilitated by a permeable porosity generated in primary Cu-Fe sulfides) are considered to be important for the remobilization and local reconcentration of early-formed precious metals, and may have been responsible for the formation of relatively coarse-grained native gold or silver within recrystallized massive sulfides and chimney debris.     

In situ zircon U–Pb dating and O isotopes of the Neoarchean Hongtoushan VMS Cu–Zn deposit in the North China Craton: Implication for the ore genesis

The Hongtoushan volcanogenic massive sulfide (VMS) deposit is the largest Archean Cu–Zn deposit in China, located in the Qingyuan greenstone belt on the northern margin of the North China Craton. The Cu–Zn mineralization was stratigraphically controlled by the interbeds (~ 100 m in thickness) of mafic–felsic volcanic sets and overlain by banded iron layers. However, the relationship between VMS deposits and associated volcanics has not been examined. This study ultimately clarifies the times and sources of the volcanics and mineralization. Based on in situ zircon U–Pb and O isotope on VMS-hosting mafic, felsic volcanic rocks, banded and massive sulfide ores and postmineralization pegmatite vein, we considered that there were two main formation stages for the Qingyuan Cu–Zn deposits; one was exhalative-hydrothermal sedimentation and another was further Cu–Zn enriched by later hydrothermal processes. The timing of the first stage occurred at 2571 ± 6 Ma based on the magmatic zircons in the VMS-hosting mafic volcanic rocks, from which the inherited zircons also indicate the existence of 2.65–3.12 Ga ancient supercrustal rocks in the Qingyuan district. A modern mantle-like δ¹⁸Ozircon value of 5.5 ± 0.1‰ (2SD) for this volcanism was well preserved in the inherited core domains of ore samples. It suggests that the mafic volcanics was most likely sourced from partial melting of juvenile crust, e.g., TTG granites. A large-scale metamorphic or hydrothermal event is documented by the recrystallized zircons in sulfide ores. The timing is tightly constrained by the hydrothermal zircon U–Pb ages. They are 2508 ± 4 Ma for the banded ore, 2507 ± 4 Ma for the massive ore and 2508 ± 2 Ma for the postmineralization pegmatite vein. These indistinguishable ages indicate that the 2507 Ma hydrothermal systems played a significant role in the upgrading of the VMS Cu–Zn orebodies. The weighted δ¹⁸O values of hydrothermal zircons show a successively increasing trend from 6.0 ± 0.1‰ (2σ) for the banded ore, 6.6 ± 0.2‰ (2σ) for the massive ore to 7.3 ± 0.2‰ (2σ) for the later pegmatite vein. This variation might be induced by gradual inputting of the δ¹⁸O-rich oceanic crust and/or oceanic sediment during the hydrothermal cycling system. Considering its modern mantle-like oxygen isotope composition of 2571 Ma volcanism, a submarine volcanic hydrothermal system involving mantle plumes is a preferred setting for the Neoarchean VMS Cu–Zn deposits in the Qingyuan greenstone belt.     

Tectonic drivers and the influence of the Kerguelen plume on seafloor spreading during formation of the early Indian Ocean

The Perth Abyssal Plain (PAP), located offshore southwest Australia, formed at the centre of Mesozoic East Gondwana breakup and Kerguelen plume activity. Despite its importance as a direct and relatively undisturbed recorder of this early spreading history, sparse geophysical data sets and lack of geological sampling hamper our understanding of the evolution of the PAP. This study combines new bathymetric profiles across the PAP with petrographic and geochemical data from the first samples ever to be dredged from the flanks of the Dirck Hartog Ridge (DHR), a prominent linear bathymetric feature in the central PAP, to better constrain the formation of the early Indian Ocean floor and the influence of the Kerguelen plume. Seafloor spreading in the PAP initiated at ~ 136 Ma with spreading observed to occur at (half) rates of ~ 35 mm/yr. Changes in spreading rate are difficult to discern after the onset of the Cretaceous Quiet Zone at ~ 120 Ma, but an increase in seafloor roughness towards the centre of the PAP likely resulted from a half-spreading rate decrease from 35 mm/yr (based on magnetic reversals) to ~ 24 mm/yr at ~ 114 Ma. Exhumed gabbro dredged from the southernmost dredge site of the DHR supports a further slowdown of spreading immediately prior to full cessation at ~ 102 Ma. The DHR exhibits a high relief ridge axis and distinctive asymmetry that is unusual compared to most active or extinct spreading centres. The composition of mafic volcanic samples varies along the DHR, from sub-alkaline dolerites with incompatible element concentrations most similar to depleted-to-normal mid-ocean ridge basalts in the south, to alkali basalts similar to ocean island basalts in the north. Therefore, magma sources and degrees of partial melting varied in space and time. It is likely that the alkali basalts are a manifestation of later excess volcanism, subsequent to or during the cessation of spreading. In this case, enriched signatures may be attributed tectonic drivers and melting of a heterogeneous mantle, or to an episodic influence of the Kerguelen plume over distances greater than 1000 km. We also investigate possible scenarios to explain how lower crustal rocks were emplaced at the crest of the southern DHR. Our results demonstrate the significance of regional tectonic plate motions on the formation and deformation of young ocean crust, and provide insight into the unique DHR morphology.     

Native antimony in the Baogutu gold deposit (west Junggar,NW China): Its occurrence and origin

The Baogutu gold deposit, West Junggar (Xinjiang, NW China), is composed of quartz–sulfide veins and their stockworks and is hosted within an Early Carboniferous volcanic–sedimentary sequence. Three ore-forming paragenetic stages can be identified: coarse-grained quartz–sulfide vein (stage I), gold-bearing fine-grained quartz–sulfide vein (stage II), and native antimony-bearing calcite–sulfide veinlets (stage III). The estimated formation temperatures (approximately 360 to 220 °C), fS₂ (? 7 to ? 15 log units), and fO₂ (? 26 to ? 43 log units) decrease from stage I, through stage II, to stage III. The nature of the hydrothermal fluid changed from weakly acidic (pH: 5 to 6 at stage I) to alkaline (pH: > 7 at stage III).Two different occurrences of native antimony could be identified: one coexists with chalcopyrite and pyrrhotite, whereas the other occurs as isolate grains within calcite veins. Native antimony (up to 100 μm in size) contains minor amounts of As (2.0 to 2.7 wt.%); empirical formula Sb_0.95–0.96As_0.03–0.04. Decrease of temperature and fO₂ at high pH and low fS₂ conditions favored co-precipitation of native antimony–ullmannite assemblages and the decomposition of tetrahedrite. Native antimony crystallized later than the native gold, suggesting fractionation between Au and Sb during the hydrothermal evolution of the deposit.     

An Early Cretaceous carbonate replacement origin for the Xinqiao stratabound massive sulfide deposit,Middle-Lower Yangtze Metallogenic Belt,China

Stratabound massive sulfide deposits are widespread along the Middle-Lower Yangtze Metallogenic Belt (MLYMB) and serve as an important copper producer in China. Two contrasting genetic models have been proposed, interpreting the stratabound massive sulfide deposits as a Carboniferous SEDEX protore overprinted by Cretaceous magmatic-hydrothermal system or an Early Cretaceous carbonate replacement deposit. These two contrasting models have been applied to the Xinqiao stratabound Cu-Au sulfide deposit, which is dominated by massive sulfide ores hosted in marine carbonates of the Carboniferous Chuanshan and Huanglong Formations, with minor Cu-Au skarn ores localized in the contact zone between the Cretaceous diorite Jitou stock and the Carboniferous carbonate rocks. New SIMS zircon U-Pb dating suggests that the Jitou stock formed at 138.5 ± 1.1 Ma (2σ, MSWD = 0.6). Pyrite Re-Os dating yields an imprecise date of 142 ± 47 Ma (2σ, MSWD = 7.8). The geochronological data thus constrain the mineralization of the Xinqiao deposit at Early Cretaceous.Fluid inclusions in prograde skarn diopside have homogenization temperatures of 450–600 °C and calculated salinities of 13–58 wt.% NaCl equiv. Quartz from the stratabound ores and pyrite-quartz vein networks beneath the stratabound ores have homogenization temperatures of 290–360 and 200–300 °C, with calculated salinities of 5–12 and 2–10 wt.% NaCl equiv., respectively. Quartz from the skarn ores and veins beneath the stratabound ores have δ¹⁸O values of 12.32 ± 0.55 (2 SD, n = 22) and 15.57 ± 1.92‰ (2 SD, n = 60), respectively, corresponding to calculated δ¹⁸O values of 6.22 ± 1.59 (2σ) and 6.81 ± 2.76‰ (2σ) for the equilibrated ore-forming fluids. The fluid inclusion and oxygen isotope data thus support a magmatic-hydrothermal origin rather than a SEDEX system for the stratabound ores, with the hydrothermal fluids most likely being derived from the Jitou stock or associated concealed intrusion. Results from this study have broad implications for the genesis and exploration of other stratabound massive sulfide deposits along the MLYMB.