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Authigenic carbonate samples were collected from the northern Okinawa Trough. Based on their carbon and oxygen isotopes, these samples were found to be methane-related carbonates precipitated by the anaerobic oxidation of methane (AOM). Petrological analysis revealed numerous framboidal pyrites that had been partly oxidized. In order to trace the variation and diagenetic information of these framboidal pyrites, their diameters and geochemical components were studied using an electron probe. The results showed that their diameters varied from 4 µm to 17 µm (n = 60; geometric mean of 9.9 µm) and were of a normal distribution. The diameters of single pyrite that formed the framboidal pyrites varied from 1 µm to 2 µm. The framboidal pyrites with diameters of 6–10 µm accounted for ~80% of the total. The geometric mean of 9.9 µm indicates that they are probably diagenetic pyrites that were precipitated in a lower dysoxic environment (weakly oxygenated bottom waters). The S/Fe ratio of the framboidal minerals ranged from 0 to 1.67, and the pyrite content of single framboid varied between 0% and 86.4%. Therefore, numerous pyrites were oxygenated to iron oxides or oxyhydroxides, and were retained as pseudomorphism pyrites. The size of framboidal pyrites precipitated in cold seeps can be used to trace the redox environment; however, acquisition of additional data via investigation of different cold seeps is necessary to obtain more persuasive results.

We present major and trace element data of lava recovered from the northern Yap Trench in the western Pacific and discuss their petrogenesis and tectonic implications within the framework of interactions between the Caroline Ridge and Yap Trench. Rocks were collected from both landward and seaward trench slopes and exhibited geochemical characteristics similar to backarc basin basalt (BABB) and mid-ocean ridge basalt (MORB), including high Fe content, tholeiitic affinity, high TiO2 value at a given FeOT/MgO ratio, Ti/V ratio between 20 and 50, low Ba/Nb ratio and Th/Nb ratio, and trace element patterns commonly displayed by BABB and MORB, which are distinct from arc lava. These rocks seem to have been generated during mantle upwelling and decompression melting at a spreading center. However, compared with typical forearc lava produced by seafloor spreading in the Mariana forearc region, such as the early Eocene forearc basalts and late Neogene forearc lava in the southernmost Mariana Trench, the Yap Trench lava is derived from a more fertile mantle and feature a more minor subduction component; thus, they cannot be the products of forearc mantle decompression melting. We suggest that the landward slope lava represents backarc basin crust that was overthrust onto the forearc lithosphere during the collision of the Caroline Ridge with the Yap Trench (20–25 Ma), which played a key role in the evolution of the Yap subduction system. Moreover, the seaward slope lava represents the subduction plate crust that accreted onto the deep trench during the collision. This collision event resulted in the cessation of Yap Arc magmatism; thus, the Yap Trench volcanic rocks (

Carbonate recycling in subduction zones has a strong influence on arc magmatism and carbon reservoirs in the mantle. However, geochemical evidence of carbonate recycling during subduction, especial...

Shallow seawater-hydrothermal circulation plays a crucial role in the subseafloor mineralization of the hydrothermal system. However, its key fluid processes and impacts on the metal mobilization and sulfur cycles in the stockwork mineralization are still poorly understood. We first present the systemic variations in micro-scale trace element and sulfur isotope compositions of pyrite varieties in a stockwork-like sulfide from the Longqi hydrothermal field to constrain the metal transport and deposition and sulfur origins and cycles in the shallow seawater-hydrothermal circulation. Pyrites considered as the dominant sulfides can be clarified into disseminated fine-grained (Py-I), euhedral (Py-II), and subhedral-euhedral (Py-III) varieties based on texture. The wall-rock-derived elements Ti, Cu, Ni, Mg, and Mn and seawater-derived elements Mo, V, and U are concentrated in Py-I within the breccias and related to the fluid-rock reaction and fluid-seawater mixing in the shallow seawater-hydrothermal circulation system. Short-lived shallow circulation results in fluid fluctuation and oscillatory-zoned Py-II with depletion of Co, Ni, Cu, As, and Se in the mantles relative to those in the rims and cores. As the later hydrothermal activity was active, Py-III that was overgrown from Py-II is rich in hydrothermally inherited metals Se, Te, and Co, possibly implying the hydrothermal field is coming into the main mineralization. The sulfur isotope compositions of pyrites range from 4.30 to 9.98‰ (n=37), with distinct δ34S variations in the individual Py-I crystal (> 1.5 ‰ within a 20 × 20 µm2 region). This variation is attributed to changes in the relative proportion of sulfur sourced from (i) the shallow-origin reduced seawater via reduction by ferrous iron released from basalt (ii) the reduction of pre-existing anhydrite by later hydrothermal overprinting in the shallow subseafloor. These findings provide evidence for a model to better understand the effect of shallow seawater-hydrothermal circulation on the subseafloor stockwork mineralization of hydrothermal fields.

Electron microprobe analysis was conducted on plagioclase from the plagioclase ultraphyric basalts (PUBs) erupted on the Southwest Indian Ridge (SWIR) (51°E) to investigate the geochemical changes in order to better understand the magmatic processes occurring under ultraslow spreading ridges and to provide insights into the thermal and dynamic regimes of the magmatic reservoirs and conduit systems. The phenocryst cores are generally calcic (An74–82) and are depleted in FeO and MgO. Whereas the phenocryst rims (An67–71) and the plagioclase in the groundmass (An58–63) are more sodic and have higher FeO and MgO contents than the phenocryst cores. The crystallization temperatures of the phenocryst cores and the calculation of the equilibrium between the phenocrysts and the matrix suggest that the plagioclase cores are unlikely to have crystallized from the host basaltic melt, but are likely to have crystallized from a more calcic melt. The enrichment in incompatible elements (FeO and MgO), as well as the higher FeO/MgO ratios of the outermost phenocryst rims and the groundmass, are the result of plagioclase-melt disequilibrium diffusion during the short residence time in which the plagioclase crystallized. Our results indicate that an evolved melt replenishing under the SWIR (51°E) drives the eruption over a short period of time.

Ferromanganese nodules are a potential energy resource because of their high contents of economically interesting elements (i.e. Mn, Ni, Cu, and Zn). These are higher in diagenetic layers than in hydrogenetic layers. The study of the causes of elemental accumulation in the diagenetic layer is useful for the exploration metal-rich nodules. A diagenetic-dominant ferromanganese nodule, from the central Clarion–Clipperton Fracture Zone of the eastern Pacific Ocean was studied from core to rim. It was divided into four layers and seven sublayers, of the four typical diagenetic sublayers (L1, L2-1, L2-2, and L3-1). Differences were observed in these diagenetic sublayers. L1 presents the highest Mn/Fe ratio (54), the lowest Co content (2262 ppm), and a positive Ce anomaly. L2-1 exhibits high Co (3122 ppm) and Ba contents (4020 ppm), a positive Ce anomaly, and an obvious peak for 10 Å manganate minerals. L2-2 contains the lowest Ni+Cu contents (3.2 wt%), the highest Ba and Co contents (5110 ppm), and the strongest positive Ce anomaly. In L2-2, the δCe value can be positively correlated to the Mn/Fe ratio and a pronounced peak for 10 Å manganate minerals indicates that this layer has the highest mineral crystallinity. L3-1 shows the highest Ni+Cu contents (5.4 wt%), the lowest Ba (1247ppm), and Co (1725 ppm), a weakly positive Ce anomaly, and the poorest mineral crystallization. Diagenetic- and hydrogenetic-endmember mixing models reveal that hydrogenetic input contributes minimally to these chemical changes, whereas diagenetic input contributes greatly. The changes in diagenetic input may be caused by the changes in primary productivity brought about by movement of tectonic plates and the intense activity of the diagenetic pore fluid. The activity may provide a metal source for the diagenetic sublayer (anomalously high Co and Ce content) via the incorporation of metals released from dissolved buried nodules and micronodules under a suboxic or reducing environments.

Manganese nodules are a potential source of critical metals such as Cu, Ni, and Co and are widely distributed on the abyssal plains of the global oceans. A polymetallic nodule metallogenic belt with a heterogeneous and spatially clustered nodule distribution was recently discovered in NW Pacific inter-seamount basin (NPIB) areas. However, the geological processes that regulate the nodule occurrence in that region are unresolved. Here, we report on the characteristics of a high-density field of manganese nodules in the abyssal plain north of Suda Seamount. Ship-borne multibeam bathymetric data reveal a typical seamount sector-collapse topography characterized by radial lineaments of debris channels and ridges formed by rapid debris-avalanche flow. Backscatter data linked with underwater observation indicate that manganese nodules are more concentrated (50%–80% areal coverage) along the main body of the debris apron compared to adjacent neighboring areas (

Dehydrated fluids expelled from serpentinized mantle in the subducted slab are gradually recognised as a vital role in generating arc magmatism and element cycling in the Earth. However, it remains not clear about their recycling at various depth in subduction zones and if slab serpentinite-derived fluids contribute to the genesis of lavas from the back-arc basins. Here, we study the magnesium (Mg) isotopic compositions of lavas from the Okinawa Trough (OT) and Lau basin (LB) as Mg isotopes have shown great potential to trace dehydration of slab serpentinites in recent years. Overall, lavas from the OT and LB have averagely heavier Mg isotopic compositions relative to the mid-ocean ridge basalt (MORB) mantle, which could be attributed to the involvement of slab serpentinite-derived fluids rather than crustal assimilation or input of subducted sediments as indicated by the isotopic modelling results. The δ26Mg values of the southern OT (SOT) and southern LB (SLB) are generally higher than the middle OT (MOT) and northern LB (NLB), respectively, with an average of -0.11 ± 0.06‰ (2SD, n=5) for the SOT, -0.20 ‰ ± 0.04 (2SD, n=5) for the MOT, -0.13 ‰ ± -0.08 for the SLB (2SD, n=6) and -0.19 ‰ ± 0.06 (2SD, n=10) for the NLB. The binary modelling results have shown that various amounts of serpentinite-derived fluids could explain the variations in Mg isotopic compositions observed in the OT and LB. Combined published δ26Mg values in subduction zones with our data, the thermal structure of inter-subduction zone may play a first control on the signal of Mg-rich serpentinite-derived fluids. By contrast, the contributions of these fluids to different segments in a specific subduction zone may depend on the slab depth beneath magmatic activity sites.

Magmatic sulfide formation and oxidative dissolution are effective in metal pre-enrichment and remobilization during magmatic processes, and are considered to be a prerequisite for the formation of magmatic–hydrothermal ore deposits in subduction zones. However, this sequential process and sulfide oxidation mechanism are poorly understood. In this study, we report fine-grained sulfides with variable degrees of oxidation distributed within mafic cumulates, brought into felsic magma as mafic magma intrusions in the southwestern Okinawa Trough. Thermodynamic modeling suggests that the oxygen fugacity (fO2) of primitive mafic magma is ∼FMQ + 2.5, reducing to ∼FMQ + 1 in evolved mafic magma and to ∼FMQ + 0.5 in felsic magma. This variation results from the continuous assimilation of reduced country rocks, as reflected by negative δ34SVCTD values (–0.62‰ ± 0.23‰) of magmatic sulfides and highly radiogenic Sr–Nd isotopic compositions of host dacite. Magmatic reduction and addition of crust-derived sulfur result in early formation of crystalline sulfides, dominantly pyrrhotite, enriched in Cu (0.93 ± 0.38 wt.%). A new injection of oxidized mafic magma triggers partial to complete oxidation of the earlier magmatic sulfides, ultimately transforming them into hematite–magnetite (HM) intergrowths. This means that sulfide oxidation is not directly associated with the mafic magma itself, but more likely with high-fO2 magmatic fluid exsolved from the primitive mafic magma. The oxidative dissolution process releases >90% of Cu from the primary sulfides, with this Cu preferentially moving into magmatic fluid. This indicates that metal remobilization and transfer is very efficient under HM buffer conditions, in which trisulfur S3− ions with high affinities for Au and Cu are probably the dominant sulfur species. We suggest that the periodic injection of oxidized mafic magma into continental crust containing reduced lithologies is essential for the sequential process of early sulfide formation and later oxidative dissolution in the Okinawa Trough and in other subduction zone settings with similar tectono-magmatic conditions. This process could be a precursor to the generation of metal-bearing magmatic fluid, contributing to mineralization in subduction zones.

A coupled approach based on grain size and geochemical elements is used to trace the provenance of surface sediments and to confirm the distribution patterns of grain size and elements on the continental shelf off western Guangdong Province and northeastern Hainan Island. The mean grain size ranges from 0.05 ϕ to 7.28 ϕ with a mean value of 5.60 ϕ. The average concentrations of major elements descend in the order of SiO2 >Al2O3 >CaO>Fe2O3 >K2O>MgO>Na2O>TiO2 >P2O5 >MnO, while those of trace elements exhibit a descending order of Sr>Rb >Zn>V>Cr>Pb>Ni>Cu>As>Cd. On the basis of the distribution patterns of elements and results of statistical analysis, the study area is classified into three zones. Zone I locates on the continental shelf off western Guangdong Province, and the sediments are mainly from Pearl River, Taiwanese rivers, and small rivers nearby. Zone II locates in the eastern exit of Qiongzhou Strait and the coastal area off Leizhou Peninsula, and the sediments are mainly from the erosion products of Qiongzhou Strait and Hainan Island. Zone III locates off the eastern Hainan Island and the continental shelf deeper than −50 m isobaths, and the sediments are mainly from Hainan Island and coral reef. The influence from open water should also be considered. Results indicate that the grain size is the main controlling factor for major and trace element contents and that anthropogenic impact and biological activity also play an important role in the distribution of these elements.

We analyze Pb content and Pb isotope ratios in 29 surface sediments and one sediment core from the eastern Beibu Gulf, Southern China. The results indicate that obvious Pb enrichment was limited to the oil and gas exploration area in the central gulf and the mud deposit in the northern gulf. The enrichment of Pb in sediment core A97 started in the 1860s, but a notable drop of Pb content occurred in the 1970s, suggesting variations in human activity. The Pb isotope ratios in sediments were very similar to those in natural sources, except for the sediments near the oil platform, which may be polluted by anthropogenic input. Sediments with relatively high radiogenic Pb isotope compositions may be mainly sourced from northern coast of Beibu Gulf, sediment flux through Qiongzhou Strait, or the Red River, while the coastal zone of western Hainan Island and nearby bottom erosion area produce as minor provenances.

A multi-index analysis including grain size, major and trace elements is performed on the surface sediments from the northeastern Beibu Gulf to trace the sources of the sediments and to understand the controlling factors for elements distribution. The mean grain size exhibits a wide variation ranging from 0.09Φ to 8.05Φ with an average value of 5.33Φ. The average contents of major elements descend in an order of c(SiO2)>c(Al2O3)>c(Fe2O3)>c(CaO)>c(MgO)>c(K2O)>c(Na2O)>c(TiO2)>c(P2O5)>c(MnO), while those of trace elements exhibit a descending order of c(Sr)>c(Rb)>c(V)>c(Zn)>c(Cr)>c(Pb)>c(Ni)>c(Cu)>c(As). On the basis of elementary distribution characteristics and statistical analyses, the study area is divided into the four zones: Zone I is located in the northeastern coastal area of the gulf, which receives large amount of fluvial materials from local rivers in Guangxi and Guangdong, China, and the Qiongzhou Strait; Zone II is located in the center of the study area, where surface sediments exhibits a multiple source; Zone III is located in the Qiongzhou Strait, where surface sediments are dominated by materials from the Zhujiang River and Hainan; Zone IV is located in the southwest of the study area, where surface sediments are mainly originated from the Red River and Hainan. The statistical analyses of sediment geochemical characteristics reveal that the grain size, which is mainly influenced by hydrodynamics and mineral composition of terrigenous materials, is the leading factor controlling the elementary distribution. Meanwhile, impacts from anthropogenic activities and marine biogenic process will also be taken into consideration.

The northern Lau back-arc basin (NLB) lavas display a diverse geochemical nature caused by complex geological processes in this region. Independent component (IC) analysis was applied to investigat...

Research on seamounts provides some of the best constraints for understanding intraplate volcanism, and samples from seamounts reveal crucial evidence about the geochemical makeup of the oceanic mantle. There are still many seamounts in the West Pacific Seamount Province (WPSP) that have not been studied, meaning their ages and geochemistry remain unknown. A better understanding of these seamount trails and their evolutionary history, investigated with age and geochemistry data, will enable better understanding of the geological processes operating underneath the Pacific Ocean Plate. Here, new 40Ar/39Ar ages and trace element and Sr-Nd-Pb isotopic data for seven basalt rocks from four seamounts in the WPSP are provided. Chemically, these rocks are all Oceanic Island Alkali basalt (OIA type); analysis of olivine phenocrysts shows that the magmas experienced strong olivine fractionation and changed from olivine + plagioclase to olivine + plagioclase + clinopyroxene cotectic during their evolution. Rare earth element (REE) patterns and a spider diagram of the samples in this study show OIB (Ocean Island Basalt) like behavior. The range of 87Sr/86Sr values is from 0.704 60 to 0.706 24, the range of 206Pb/204Pb values is from 18.241 to 18.599, and the range of 143Nd/144Nd values is from 0.512 646 to 0.512 826; together, these values indicate magma sources ranging from EMI to EMII. Finally, new 40Ar/39Ar age data show that these seamounts formed at ~97 and ~106 Ma, indicating that some may have undergone the same formation processes as seamounts in the eastern part of the Magellan Seamount Trail, but other seamounts likely have different origins.

Methane-derived carbonates with blocky and chimney morphologies were collected on the northern slope of the South China Sea. The studies of petrography, geochemistry and chronology show that the blocky carbonate has a microcrystalline structure with numerous of biogenic tests, whereas the carbonate chimney has a cryptocrystalline structure with scarce biogenic tests. Aragonite can be detected in the carbonate chimney, which indicates that it formed at the shallow sediments or on the seafloor. The δ13C and δ18O values of the blocky carbonate range from −46.8‰ to −28.8‰ VPDB and 2.2‰ to 3.5‰ VPDB, respectively. The δ13C and δ18O values of the carbonate chimney range from −45.0‰ to −22.9‰ VPDB and −2.8‰ to 3.1‰ VPDB, respectively. The carbon isotopic values indicate that these carbonates are related to the anaerobic oxidation of methane (AOM). The oxygen isotopic values show that the gas hydrate dissociation contributed the 18O-enrich fluid to a certain degree during the authigenic carbonate formation. According to the rare earth element results, the carbonate chimney precipitated in stable anoxic conditions. Because of the La-enriched influence, the formation environment of the blocky carbonate is ambiguous. The U/Th chronology results indicate that these authigenic carbonates precipitated during the last glacial period (primarily Marine Isotopic Stage 3) of low sea level stand.

Sulphur isotopes can be used as a powerful tool to trace fluid evolution and explore the formation of chimneys. To clarify the in situ S isotopic variations of sulphides at the micro-scale, we analyzed a sulphide chimney collected from the hydrothermal field in the East Pacific Rise 1–2° S using a sensitive high-mass-resolution ion micro-probe for stable isotopes (SHRIMP SI). Three mineral zones can be identified in the chimney: an external outer wall of porous anhydrite and colloform pyrite, an internal middle zone of sub-euhedral pyrite and massive chalcopyrite, and an inner zone of massive pyrite. The δ34SV-CDT values of the sulphides fall within the range 1.83–7.51 ‰ (avg. 4.05 ‰, n = 16), and S isotopic values increase from the core (3.09 ‰, n = 3) to the middle (3.78 ‰, n = 11) to the edge (6.99 ‰, n = 2). These results illustrate mineral crystallization processes and the mixing between seawater-derived S and magmatic–hydrothermal fluids during the growth of the chimney. The zones from the edge to the core are characterized by crystal morphologies of colloform/anhedral pyrite to massive pyrite with decreasing δ34S values, revealing multi-stage mineral deposition and sulphur isotopic fractionation. In contrast to the increase in δ34S values from the core to the edge in one profile (profile A), anomalously low δ34S values in fine-grained pyrite relative to chalcopyrite in another profile (profile B) in the middle zone result from S isotopic exchange between seawater SO42− and fluid H2S due to different fluid–seawater mixing, possibly caused by variations in permeability and porosity across the chimney.

The 15.2°S hydrothermal field is located at 15.2°S, 13.4°W within the Mid-Atlantic Ridge (MAR) and was initially discovered during Cruise DY125-22 by the Chinese expedition during R/V Dayangyihao in 2011. Here, we provide detailed mineralogical, bulk geochemical, and Sr–Pb isotopic data for massive sulfides and basalts from the 15.2°S hydrothermal field to improve our understanding of the mineral compositions, geochemical characteristics, type of hydrothermal field, and the source of metals present at this vent site. The samples include 14 massive sulfides and a single basalt. The massive sulfides are dominated by pyrite with minor amounts of sphalerite and chalcopyrite, although a few samples also contain minor amounts of gordaite, a sulfate mineral. The sulfides have bulk compositions that contain low concentrations of Cu + Zn (mean 7.84 wt%), Co (mean 183 ppm), Ni (mean 3 ppm), and Ba (mean 16 ppm), similar to the Normal Mid-Ocean Ridge Basalt (N-MORB) type deposits along the MAR but different to the compositions of the Enriched-MORB (E-MORB) and ultramafic type deposits along this spreading ridge. Sulfides from the study area have Pb isotopic compositions (206Pb/204Pb = 18.4502–18.4538, 207Pb/204Pb = 15.4903–15.4936, 208Pb/204Pb = 37.8936–37.9176) that are similar to those of the basalt sample (206Pb/204Pb = 18.3381, 207Pb/204Pb = 15.5041, 208Pb/204Pb = 37.9411), indicating that the metals within the sulfides were derived from leaching of the surrounding basaltic rocks. The sulfides also have 87Sr/86Sr ratios (0.708200–0.709049) that are much higher than typical MAR hydrothermal fluids (0.7028–0.7046), suggesting that the hydrothermal fluids mixed with a significant amount of seawater during massive sulfide precipitation.

Significant Fe isotopic fractionation occurs during the precipitation and oxidative weathering of modern seafloor hydrothermal sulfides, which has an important impact on the cycling of Fe isotopes in the ocean. This study reports the Fe-isotope compositions of whole-rock sulfides and single-mineral pyrite collected from hydrothermal fields at the South Mid-Atlantic Ridge (SMAR) and the East Pacific Rise (EPR) and discusses the impacts of precipitation and late-stage oxidative weathering of sulfide minerals on Fe isotopic fractionation. The results show large variation in the Fe-isotope compositions of the sulfides from the different hydrothermal fields on the mid-oceanic ridges, indicating that relatively significant isotope fractionation occurs during the sulfide precipitation and oxidative weathering processes. The Fe-isotope compositions of the sulfides from the study area at the SMAR vary across a relatively small range, with an average value of 0.01‰. This Fe-isotope composition is similar to the Fe-isotope composition of mid-oceanic ridge basalt, which suggests that Fe was mainly leached from basalt. In contrast, the Fe-isotope composition of the sulfides from the study area at the EPR are significantly enriched in light Fe isotopes (average value − 1.63‰), mainly due to the kinetic fractionation during the rapid precipitation process of hydrothermal sulfide. In addition, the pyrite from different hydrothermal fields is enriched in light Fe isotopes, which is consistent with the phenomenon in which light Fe isotopes are preferentially enriched during the precipitation of pyrite. The red oxides have the heaviest Fe-isotope compositions (up to 0.80‰), indicating that heavy Fe isotopes are preferentially enriched in the oxidation product during the late-stage oxidation process. The data obtained from this study and previous studies show a significant difference between the Fe-isotope compositions of the sulfides from the SMAR and EPR. The relatively heavy Fe isotopes compositions of the sulfides from the SMAR may suggest the equilibrium fractionation process under high temperature conditions. The red Fe oxides are enriched in heavy Fe isotopes, indicating that the oxidative weathering processes result in the occurrence of significant Fe-isotope fractionation and the preferential enrichment of heavy Fe isotopes in the oxidation product.

The weathering processes of seafloor massive sulfide (SMS) deposits would significantly change the mineralogy and geochemistry of sulfides. The key to understanding the oxidation of SMS deposits lies in clarifying the metal mobilization during the oxidation of submarine sulfides by seawater and Fe-Si-rich hydrothermal fluids. We present the morphology, mineralogy, and geochemistry of secondary minerals and oxyhydroxides from the Xunmei hydrothermal field on the Southern Mid-Atlantic Ridge (SMAR) to illuminate their diverse characteristics and origins, further elaborating detailed submarine oxidation processes of sulfide mounds. Under the oxygenated seawater environments, the pyrite/marcasite and chalcopyrite were oxidized to Fe (oxyhydr)oxides and secondary Cu minerals (e.g., covellite, paratacamite/atacamite, and chalcanthite), respectively. The metal speciation in the sulfides (e.g., pyrite, marcasite, and chalcopyrite) controls the metal mobilization during oxidation. Cobalt and As in the crystal lattice of pyrite and marcasite vary over variations in Fe and S, respectively. Zinc, Ag, and Pb that occur as micron-inclusions in the pyrite, marcasite, and chalcopyrite are easily released during the galvanic interaction, of which mechanism is applicable to Cu-inclusions in the pyrite and marcasite. Compared to the enrichment of Zn and Ag in the secondary minerals via adsorption, Pb is depleted because of its high solubility in the seawater. The mineralization of amorphous oxyhydroxides includes low-temperature Si-rich precipitation and later oxidative weathering processes. The Si-rich hydrothermal fluids dissolve the basalt enriched in plagioclase and V-rich clay minerals to precipitate V-rich Si-Al oxyhydroxides. Subsequently, the flowing Si-rich hydrothermal fluids evoke precipitation of amorphous silica due to conductive cooling. As the alteration proceeds, a genetic scenario for the formation of Fe and Si oxyhydroxides is proposed. The Fe-Si-rich hydrothermal fluids alter the sulfides to Fe-Si oxyhydroxides and then Fe oxyhydroxides with an increasing trend of Fe, Cu, Zn, and Co. Our results unravel the metal mobilization during the weathering processes of submarine sulfides, establish a scenario for the formation of oxyhydroxides associated with sulfides, and predict the effect of oxidation on the economic values of sulfides.

Crustal assimilation and the input of subducted sediment in a subduction zone play vital roles in generating arc and back-arc lavas along a continental margin. However, distinguishing the impacts of these two processes on lava geochemistry is not straightforward or well understood. In this paper, we present new Hf–Nd–Sr–Pb isotopic data for 20 igneous rocks ranging in composition from basalt to rhyolite, which when combined with data from the literature allow us to fingerprint the contributions of crustal and slab-derived materials along the Okinawa Trough (OT). Consistent with previous results, the basaltic lavas were generated by melting of an Indian-type mantle source metasomatised by slab-derived fluids and subducted pelagic/detrital sediments. We confirm that Hf behaves as a non-conservative element during subduction, constrained by Hf-Nd isotopic systematics. Our new data suggest that crustal assimilation processes worked independently of the extent of magma differentiation but were determined by the stage of tectonic development in individual regions. In the southern OT (seafloor spreading stage), crustal assimilation is insignificant, and the addition of subducted sediment is 0.4%–1.5%. In the middle OT (crustal rifting stage), the basaltic and rhyolitic suites do not show distinctive Hf–Nd–Sr–Pb isotopic compositions, and both record moderate crustal assimilation (

Discontinuities in the magmatic activity along a spreading ridge are usually observed in ultraslow-spreading ridges with a thick crust. However, the reasons for such melting anomaly are unknown. The Dragon Flag Supersegment between the Indomed Fault Zone (FZ) and the Gallieni FZ on the Southwest Indian Ridge (SWIR) is characterised by ultra-thick oceanic crust (up to ~10 km), and it provides a unique opportunity for studying magmatic crustal accretion at an ultraslow-spreading ridge. We determined the compositions of olivine–spinel pairs in mid-ocean ridge basalts (MORBs) collected from Segments 25 and 28 of the SWIR to estimate the temperatures of crystallisation and investigate the source lithologies. The olivine-spinel pairs were carefully screened and only those having crystallized in equilibrium were used for the temperature estimates. The Al-in-olivine thermometer provided crystallisation temperatures that ranged from 1197 ± 37 to 1393 ± 21 °C. The 95th percentile calculated temperature (1345 °C) for the primitive olivine is ~75 °C hotter than for olivines in MORBs from normal ridges but comparable to the data for plume-related oceanic island basalts. The olivines have Fe/Mn ratios and Ni, Ca, and Mn contents that are similar to those of olivines in MORBs from normal ridges, which suggests their derivation from a peridotite-dominant source with little contribution from fertile mantle components. Our results suggest a hot mantle reservoir is present beneath the Dragon Flag Supersegment, and that it is probably related to a mantle plume.

Significant Zn isotope fractionation occurs during seafloor hydrothermal activities. Therefore, exploring variations in Zn isotope composition affected by hydrothermal fluids and oxidative processes would help to better understand hydrothermal fluid cycling and sulfide deposition on mid-ocean ridges. In this paper, the Zn isotope compositions of different types of sulfides and their oxidation products obtained from hydrothermal fields on the South Mid-Atlantic Ridge (13–15°S) were analyzed using a Neptune plus MC-ICP-MS. The δ66Zn ratios range from –0.14‰ to +0.38‰, and the average δ66Zn ratio is +0.12±0.06‰ (n=21, 2 SD) for all the studied sulfides and oxidation products. The Cu-rich sulfides have a slightly heavier Zn isotope composition (average δ66Zn=+0.19±0.07‰, n=6) than the Zn-rich sulfides (average δ66Zn=–0.02±0.06‰, n=5). The Zn isotope compositions of the oxidation products are similar to those of the Cu-rich sulfides, with an average δ66Zn ratio of 0.14±0.06‰ (n=10, 2 SD). The Zn isotope compositions of all the samples are generally within the ranges of sulfides from hydrothermal fields on other mid-ocean ridges, such as the East Pacific Rise (9°N, 21°N) and the Trans-Atlantic Geotraverse. However, the average Zn isotope composition indicates the presence of significantly lighter Zn isotopes relative to those reported in the literature (average δ66Zn=+0.39‰). The significant enrichment of the Zn-rich sulfides with light Zn isotopes reveals that kinetic fractionation likely occurs during mineral deposition. Furthermore, the Zn isotope compositions of the sulfides and their oxidation products (average δ66Zn=+0.12‰) are significantly lighter than the average Zn isotope composition of the ocean (δ66Zn=+0.5‰), which could further constrain the modern Zn isotope cycle in the ocean by serving as a sink for light Zn isotopes.

Lipid biomarkers were investigated to reveal the microbial life preserved in sulfide and Si-rich chimney from the 49.6°E hydrothermal vent field. In sulfide chimney, iso-/anteiso-fatty acids and H-shaped glycerol dialkyl glycerol tetraethers are the main microbial biomarkers. In Si-rich chimney, monounsaturated fatty acids (C16:1n7, C18:1n7) are the main bacterial biomarkers detected, and crenarchaeol and its isomer are relatively abundant (up to 25% of glycerol dialkyl glycerol tetraethers) archaeol biomarkers. Composition of lipid biomarkers reveals the diversity of microbial communities in different types of chimney structures. Sulfate-reducing bacteria and hyperthermophilic archaea were considered to be the majority microbial life in sulfide chimney, and sulfur-oxidizing bacteria were abundant in Si-rich chimney while archaea in Si-rich chimney and mainly attributed to Thaumarchaeota, which were predominately ammonia oxidizers. Our result suggested that fluid temperature and gaseous components...

The relationship between the East Asian winter monsoon (EAWM) and East Asian summer monsoon (EASM) during the Holocene is complicated and remains controversial. In this study, analysis of grain size and benthic foraminiferal oxygen isotope, as well as accelerator mass spectrometry 14C dating was performed on a sediment core retrieved from the newly revealed muddy deposit on the northern South China Sea continental shelf. The history of the EAWM and EASM were reconstructed for the last 8200 a BP. Further analysis in conjunction with previously published paleo-climate proxies revealed that the relationship between the EAWM and EASM during the Holocene is more complex than a simple and strict anti-phase one-both negative and positive correlations were identified. The EAWM and EASM are negatively correlated around 7500, 4800, 4200, 3200, and 300 a BP (cooling periods), while positively correlated around 7100, 3700, and 2100 a BP (warm periods). In particular, both the EAWM and EASM intensified during the three positive correlation periods. However, we also found that the relationship between these two sub-monsoons is anti-phase during the final phase of particularly hot periods like Holocene Optimum and Medieval warm period. The possible impact from variations of solar irradiance on the relationship between the EAWM and EASM was also discussed.

It has long been recognized that magmatic fluids exsolved from the arc-like submarine magmas of immature back-arc basins can directly contribute metals such as Cu and Au to seafloor hydrothermal systems. The extent of this magmatic contribution, however, varies from basin to basin. In order to explain this variation, we make a comparative study of the behavior of Cu during magma differentiation in two immature back-arc ridges: Eastern Ridge (ER) of the Manus Basin and Valu Fa Ridge (VFR) of the Lau Basin. We investigate some of the factors that affect Cu behavior, including oxygen fugacity ( f O 2 ), water content, and crystallization pressure, by means of a geochemical model. Cu abundances show a continuous decreasing trend with magma evolution in the VFR lavas, whereas in the ER lavas Cu increases during the early stage of magma evolution, followed by a rapid decrease. The contrasting Cu behavior for the two lava suites is controlled on the first order by the f O 2 of their primary magmas. The f O 2 values of the primary ER magmas were modeled to be FMQ + 1.2 to FMQ + 1.8, which is sufficiently high to avoid the early sulfide saturation that typically accompanies Cu removal. By comparison, the f O 2 values of the primary VFR magmas range from FMQ to FMQ + 1, falling within the range of mid-ocean ridge basalts. We attribute this difference in f O 2 values between the primary ER and VFR magmas to variable input of sediment melt to their mantle sources. In addition, we show for the first time that Cu content does not increase significantly until the onset of plagioclase crystallization. This finding suggests that both high water contents and high pressure, which suppress plagioclase crystallization, are unfavorable for Cu enrichment in evolved oxidized magmas. We argue that back-arc ridges that develop shallow submarine magma chambers and have a large input of subducted sediment, have a strong potential to support ore-bearing magmatic–hydrothermal systems.

Hydrothermal materials in deep-sea sediments provide a robust tracer to the localized hydrothermal activity at mid-ocean ridges. Major, trace and rare earth element (REE) data for surface sediments collected from the ultraslow spreading Southwest Indian Ridge are presented to examine the existence of hydrothermal component. Biogenic carbonate oozes dominate all the sediment samples, with CaO content varying from 85.5% to 89.9% on a volatile-free basis. The leaching residue of bulk sediments by ~5% HCl is compositionally comparable to the Upper Continental Crust (UCC) in SiO2, Al2O3, CaO, MgO, alkali elements (Rb, Cs) and high field strength elements (Nb, Ta, Zr, Hf, Ti). These detritus-hosted elements are inferred to be prominently derived from the Australian continent by means of eolian dust, while the contribution of local volcaniclastics is insignificant. In addition, the residual fraction shows a clear enrichment in Fe, Mn, and Ba compared with the UCC. Combining the positive Eu anomaly of residual fraction which is opposed to the UCC but the characteristic of hydrothermal fluids and associated precipitates occurred at mid-ocean ridges, the incorporation of localized hydrothermal component can be constrained. REE mixing calculations indicate that more than half REE within the residual fraction (~55%–60%) are derived from a hydrothermal component, which is inferred to be resulted from a diffuse fluid mineralization. The low-temperature diffuse flow may be widely distributed along the slow-ultraslow spreading ridges where crustal faults and fissures abound, and probably have a great mineralization potential.

Factorial kriging analysis is applied to the research on the spatial multiscale variability of heavy metals in submarine. It is used to analyze the multiscale spatial structures of seven heavy metals, Ni, Cu, Zn, Pb, Cr, As and Cd in the surface sediment from the northeastern of Beibu Gulf, identify and separate spatial variations at different scales of heavy metals, and discuss the provenance of heavy metals and the influencing factors. The results show that the existence of three-scale spatial variations those consist of nugget effect, a spherical structure with range of 30 km (short-range scale) and a spherical structure with range of 140 km (long-range scale) in the linear model of coregionalization fitted. The spatial distribution features of seven heavy metals at short-range scale reflect “spot-like” or “stripe-like” local-scale spatial variations; the spatial distribution features of the seven heavy metals at long-range scale represent “slice-like” regional-scale spatial variations. At local scale, Zn, Cr, Ni, Cu, Pb and Cd are derived primarily from parent materials of Hainan Island, Leizhou Peninsula and Guangxi land, whose spatial distribution characteristics are controlled by granularity of sediments, while As is influenced dominantly by human pollution components from Hainan Island and Leizhou Peninsula. At regional scale, Zn, Cr, Ni and Cu originate primarily from parent rock materials of Leizhou Peninsula and Hainan Island, secondly from Guangxi land; As originated primarily from parent rock materials from Hainan Island, secondly from Leizhou Peninsula and Guangxi land. These metals are transported and migrated with sediments dominated by the anticlockwise circulation of Beibu Gulf year-round, deposited in “convergence center”, forming the whole sedimentary pattern in direction of NWW-NNW at regional scale. The difference in distribution type between As and other metals at regional scale is mainly due to their different geochemical behavior.

The Okinawa Trough (OT), is a back-arc basin where rifting is in its initial stages, and where hydrothermal fields (HTFs) have developed above terrigenous sediments and volcaniclastics layers of variable thickness. The source of ore-forming materials within the hydrothermal systems of the OT is complex, and may include seawater, magmatic rock, magmatic fluid, and sediments. The contribution of magmatic fluids and sediments to the hydrothermal systems of the OT is still uncertain. At least 10 modern seafloor HTFs have been reported from the OT, including the Jade, Hakurei, Iheya North Knoll, CLAM, Tangyin, Yonaguni Knoll IV, Hatoma, and Irabu. Here, we report results of mineralogical, geochemical, and whole-rock Sr–Pb and in situ S isotopic analyses of hydrothermal precipitates from the Tangyin HTF in the southern OT. This field was discovered during the HOBAB3 cruise in 2014 and contains four types of hydrothermal precipitates: Fe–Zn- and Zn–Pb-rich massive sulfides, silica-rich precipitates, and native sulfur-rich samples. Sulfates in Zn–Pb-, Fe–Zn-, and silica-rich samples have 87Sr/86Sr ratios of 0.71068–0.71750, which are higher than those of modern seawater and magmatic rocks, and indicate that the Sr is derived mainly from seawater and sediments. The Zn–Pb-, Fe–Zn-, and silica-rich samples have 206Pb/204Pb (18.5129–18.5307), 207Pb/204Pb (15.6374–15.6489), and 208Pb/204Pb (38.8759–38.9113) ratios that are intermediate between sediments and magmatic rocks, suggesting the Pb is a mixture of sediment- and magmatic-rock-derived Pb. The in situ S isotopic data indicate that the ore-forming fluids associated with all sample types had low δ34S values, with the Fe–Zn- (mean δ34S = 1.27‰ ± 1.38‰; SD, n = 12) and Zn–Pb-rich (mean δ34S = 0.93‰ ± 0.32‰; n = 36) massive sulfides, and silica-rich precipitates (mean δ34S = 2.85‰ ± 1.14‰; n = 58) having lower δ34S values than those of native sulfur-rich samples (mean δ34S = 4.23‰ ± 0.72‰; n = 5). The Zn–Pb- and Fe–Zn-rich massive sulfides, and silica-rich precipitates represent the medium–high temperature (>120 °C) early–middle stages of mineralization, formed under reducing conditions at low sulfur fugacity (fS2), based on the occurrence of low-fS2 mineral assemblages (e.g. high-Fe sphalerite ± isocubanite ± pyrrhotite). The low δ34S values of these three types of samples, and of the Hakurei and CLAM HTFs with low-fS2 mineral assemblages and low concentrations of Cu, Bi, and Au, most likely reflect the incorporation of biological sulfur previously formed by MSR within the sediments. The native sulfur-rich samples of the Tangyin HTF formed at low temperatures (

Active black smokers represent important products of seafloor hydrothermal systems and can reveal the fluid evolution and ore genesis in sulfide deposits. The key for understanding the details of fluid circulation and mineralization within sulfide zonation of chimneys lies in the understanding of variation in micro-scale trace elements and sulfur isotopes in sulfide deposits. An active pyrite-dominated chimney collected from the East Pacific Rise 1-2°S hydrothermal field supplies a unique opportunity to exhibit on-going ore-forming processes, especially the detailed fluid processes among the sulfide zonation of chimney, as well as to constrain the mineralization environment that is crucial for metal transport and deposition across the chimney. Pyrites, as the ubiquitous sulfide, present crystal morphologies varying from anhedral though euhedral to massive textures at different mineralization stages. The characterization of trace elements in different types of pyrite, from rim to core, evolves from Zn, Pb, Cd, Tl, Ag, Mn and Ba to Cu, Se, Sn, Bi, Co and Ni in response to increasing mineralization temperature. The dominant control on Co and Ni contents in pyrite from the exterior and interior of the chimney changes from temperature to sulfur fugacity as the hydrothermal circulation becomes active and subsequently wanes. In addition to the physicochemical environment, the chemical variations like As, Sb and Mo in pyrite from different mineral zonation are mostly like related to the temporal evolution of fluid compositions. Seawater-fluid mixing not only influences seawater-derived species of trace elements like V and Mg, and the spatial distributions of temperature-sensitive elements like Co, Cu, Se and Sn, but also increases the S isotope values of pyrite in the mineral sequence of the chimney. However, the incorporation of approximately 8 ∼ 24% bacteria-derived S leads to anhedral pyrite with abnormally light S isotopes in the outer mineral zonation.

We assess the distribution of gold and investigate the physicochemical controls on gold enrichment in the Okinawa Trough, an immature back-arc basin. We conducted a systematic study of gold and other trace-element concentrations using in situ laser ablation–inductively coupled plasma–mass spectrometry (LA–ICP–MS) for various minerals in hydrothermal sulfide samples from the Iheya North Knoll and the Yonaguni Knoll IV hydrothermal fields. Orpiment, colloform pyrite, and colloform sphalerite are relatively enriched in Au (mean contents of 30.60, 17.48, and 8.68 ppm, respectively) compared with gold-poor massive chalcopyrite, sphalerite, and pyrite. Based on gold budget estimation, colloform pyrite is the most important Au host, followed by colloform sphalerite and orpiment, with these three minerals containing the majority of gold in hydrothermal sulfides. Gold occurs as “invisible” in host minerals: as lattice-bound and submicron inclusions in colloform pyrite, as homogeneously distributed lattice-bound or nano-inclusions in colloform sphalerite, and generally as lattice-bound in orpiment and tetrahedrite. Three sets of gold host minerals are identified with distinct ore-formation temperatures. Colloform sulfides and orpiment incorporate the majority of gold at low temperatures, whereas tetrahedrite and massive sulfides incorporate only minor or trace amounts of gold at medium and high temperatures, respectively. Our results show that gold enrichment in Si–Ba–Fe-rich hydrothermal sulfides at low temperatures is a significant contributor to gold enrichment in hydrothermal sulfide deposits in the Okinawa Trough, along with the more common Zn- and Cu-rich hydrothermal sulfides. Thermodynamic modeling calculations suggest that the near-neutral pH of hydrothermal fluids and the dominant transport species, namely Au–HS complexes rather than Au–Cl complexes, are likely responsible for gold enrichment in low-temperature mineral assemblages in hydrothermal precipitates from the Okinawa Trough.

Surface sediments collected from the continental shelf off the western Guangdong Province and northeastern Hainan Island are analyzed for selected heavy metals contents including Cd, Cr, Cu, Pb, Zn, and As to determine spatial distribution, potential ecological risks, and sources. In addition, some of the controlling factors of heavy metals distribution are also discussed. The average heavy metals contents decrease in the order of Zn &gt, Cr &gt, Pb &gt, Cu &gt, As &gt, Cd. The averaged pollution degree, as shown by the index of geo-accumulation (Igeo), decreases in the order of Zn &gt, Cd &gt, As. Due to the barrier of islands, the Igeo values of Zn, Pb, Cr, Cu, and Cd near the Hailing and Xiachuan Islands are larger than those in other areas. Meanwhile, the Igeo value of As near the coastal area off the estuary of Wanquan River is clearly larger than that in other areas. Based on the results of potential ecological risk index, Cd, Cu, and As should be paid more attention for the contamination risk in future. The results of Pearson correlation analysis and principal component analysis indicate that Zn, Cr, Pb, Cu, and Cd are mainly from the Pearl River and surrounding small rivers, whereas As originates from the Hainan Island. The grain size is one of the main controlling factors for heavy metals distribution, and the anthropogenic activity also plays an important role.

This study examines the geochemistry of major and trace elements of abyssal peridotites from the Southwest Indian Ridge (SWIR) (53° E amagmatic segment), to determine the influence of mafic melts on mantle peridotites during melt extraction. The results show a great geochemical variability in the ~90 km-long ridge segment, with a degree of mantle melting ranging from 4% to 24%. An ancient melting event may explain the presence of highly depleted peridotites at the ultraslow-spreading ridge. The 53° E segment peridotites show enrichment of light rare earth elements (LREEs) (average LaN/SmN = 1.87) and significant positive anomaly of U and Pb normalized to primitive mantle (PM). The positive correlations between LREEs (La, Ce, Pr, Nd) and high field strength elements (HFSEs; e.g. Nb and Zr) suggest that the enrichment of LREEs is caused by melt refertilization, which is also supported by prevalent magmatic microstructures in the peridotites. The melt refertilization model shows that the addition of 0.02–2.7...