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Figures S1–S4

The Qiongdongnan Basin is one of the target areas for marine gas hydrate exploration in the northern margin of the South China Sea. In this study, major anion (e.g., SO4−2, Cl, Br, I), cation (e.g., Ca, Mg, K, Na), and trace element (e.g., Sr, Ba) concentrations of pore water samples collected from site HQ-1PC in the Qiongdongnan Basin were analyzed. These geochemical data suggest that the process of AOM (Anaerobic Oxidation of Methane) is dominant in sulfate-reduction zone in this site due to high upwelling iodine flux and strong microbial activities. The iodine-rich fluids, which may carry methane for the gas hydrate formation, pass through the gas hydrate stability zone, mix with brine released during gas hydrate formation, and cause the geochemical anomalies observed at site HQ-1PC. The pore water geochemical characteristics and anomalies in the Qiongdongnan Basin are quite similar to those found in other gas hydrate locations in the Shenhu area in the northern South China Sea, and a genetic link is suggested with the possibility of gas hydrate occurrence in the study area.

Taking the Himalayan granitoids around Kunjirap in the western Qinghai-Tibet plateau as an example, the authors present in this paper the characteristics of the granitoids rich in mantle-derived fluid components and discuss their rock-forming mechanism. The research results indicate that the rock assemblage of the studied granitoids involves diopside syenite-diopside granite-biotite (monzonitic) granite, consisting mainly of K-feldspar, oligoclase, quartz, iron-phlogolite, diopside and edenite. The rocks are rich in mantle-derived fluid components of volatiles including F, alkali metal elements such as K, Na, Rb, Sr and Ba, and radiogenic heat-producing elements such as U and Th. They were generated by the influx of mantle-derived fluids into the lower crust to give rise to partial melting during the lithosphere thinning in the Qinghai-Tibet plateau.

Series of sedimentary hydrothermal-diplogenetic copper deposits have been found scattering in the region along the middle-lower reaches of the Yangtze River, and their metallogenetic mechanism is still in hot debate. In order to reveal the ore-forming kinetics of sedimentary process and hydrothermal superimposition, and evaluate the role of sedimentary pyrite in the enrichment and precipitation of copper, a set of simulating experiments on the reaction between pyrite and CuCl2 solution were conducted. According to the physicochemical characteristics of the ore-forming fluid of the Dongguashan copper deposit, Anhui Province, 100 MPa was selected as the experimental pressure, and the experimental temperatures were set at 450, 350, 250 and 150°C, respectively. The reactions between pyrite grains isolated from the Shimenkou strata-bound pyrite deposit and the solution with 0.2 mol/L CuCl2 and 1.0 mol/L NaCl were experimentally simulated. Then, variations in surface topography and surface chemistry of the experimental pyrite grains were documented using scanning electronic microscopy (SEM), atomic force microscopy (AFM), Auger electron spectrometry (AES) and X-ray photoelectron spectroscopy (XPS), and the solution and newly formed minerals were analyzed using inductively coupled plasma (ICP-AES) and X-ray diffraction (XRD) techniques. Desulphurization of pyrite surface was observed and new copper minerals were detected. It is proposed that pyrite can act as a geochemical barrier for the enrichment and precipitation of copper from the solution under the experimental conditions. Furthermore, the ore-forming mechanism of sedimentary hydrothermal-diplogenetic copper deposits was discussed.

There exists an E-W trending Middle Jurassic volcanic zone in southern China. The Fankeng basalts in the Yongding basin of Fujian Province are considered to be a typical example. The Fankeng basalts have TiO 2 contents in the range of 1.92%－3.21%. They are classified as high-Ti basalts. They also have higher total Fe (averaging FeO * = 11.09%). The Middle Jurassic Fankeng basalts from southwestern Fujian have obvious distinctive lithogeochemical features from early Cretaceous basalts from southeastern coast of China. They have higher HFSE, such as Th, Nb, Ta, Zr and Ti. Their element ratios related with HFSE, such as Zr/Ba, La/Nb, La/Ta ,Zr/Y, Ti/Y, Ba/Nb, K/Ti and Rb/Zr are similar to those of OIB. The most samples have e Nd( T ) of -0.70－0.24, which are near chondrite. Some samples have higher e Nd( T ) of 1.87－3.55.Therefore, these basaltic magmas might be derived from depleted asthenospheric mantle. The lithogeochemical characteristics of the Fankeng basalts may be caused by interaction between asthenosphere and lithosphere at the time. The (Early-) Middle Jurassic basalts and gabbros from southeastern Hunan, southern Jiangxi and northern Guangdong provinces show similar geochemical features to those of the Fankeng basalts from the Yongding of Fujian. Occurrence of these OIB-type basalts in the area may be regarded as the petrological mark of upwelling of asthenosphere at the time. Upwelling of asthenosphere has led to tectonic extension and the formation of rifted basin in the area.

Magmatism in SE China was dormant during 204–180 Ma, but was reactivated in 180–170 Ma (early J2), and then became more and more intensive towards the end of early Cretaceous. The small-scale early J2 magmatism is the incipience to long-term and large-scale magmatism in this region. A near east-west (EW) trend volcanic belt was distributed across south Hunan, south Jiangxi and southwest Fujian was formed during early J2 time. Along this belt from the inland toward the coast, the lithology of basalts changes from alkali into tholeiite, and the amount of erupted volcanic rocks and the proportions of rhyolites coexisting with the basalts increase. On the basis of geochemical characteristics of these basalts, we infer that the melting degree of source rocks and the extent of fractional crystallization and crustal contamination all increased whereas the depth of mantle source decreased from the inland to the coast, which led to the variations of geological characteristics of the volcanic belt. In early J2, the western spreading Pacific plate began to subduct underneath SE China continental block, reactivating near EW trend deep fault that was originally formed during the Indosinian event. The stress of the western spreading Pacific plate and the extent of asthenosphere upwelling increased from the inland to the coast, which is consistent with the generation and evolution of early J2 basalts.

The Luxi-Xianrenzhang diabase dikes were emplaced into the eastern part of the Guidong composite granitoids in northern Guangdong Province at the end of the Early Cretaceous. They show tholeiitic features, enrichment in large ion lithophile elements, slight enrichment in light rare earth elements, depletion in Zr and Hf, and basically no depletion in Nb and Ta and no Eu anomaly. They are similar to intraplate basalt in terms of trace element characteristics. They have high ɛ Nd(t) values (3.6-4.9), initial 87Sr/86 Sr ratios (0.70530-0.70641) and δ18 O values and Dupal anomaly of Pb isotope compositions. Their Sr-Nd, Pb-Sr, Pb-Nd and Pb-Pb isotopes plot between DMM and EMII, with Pb similar to EMII, Nd relatively close to DMM and Sr in between. This profile suggests that the diabase dikes studied were derived from partial melting of a mantle source that had been subjected to metasomatism by fluids originated from a subduction zone under a tectonic environment of crustal extension and lithosphere thinning in the late Yanshanian.

Understanding the pre-anthropogenic Pb cycle of central North Pacific deep water has attracted a lot of attention in recent years, partly because of its unique geographical location in that it is a remote gyre system characterized by high dust fluxes and sluggish overturning circulation. However, the factors controlling Pb isotope evolution in this area over the Cenozoic are still controversial and various mechanisms have been proposed in previous studies. Here we report new Pb and Nd isotope time series of four ferromanganese crusts (two from the western Pacific near the Mariana arc and the other two from the central Pacific). Together with previously published records, we discuss for the first time the significance of a persistent and systematic Pb isotopic provinciality recorded by central North Pacific crusts over the Cenozoic. We propose that globally well mixed stratosphere volcanic aerosols could contribute Pb but have not been the major factors controlling the Pb isotope distribution in the central North Pacific over time. Island arc input (and probably enhanced hydrothermal input between about 45 and 20 Ma) likely controlled the Pb isotope provinciality and evolution prior to ~20 Ma, when coeval Pb isotope records in different crusts showed large differences and atmospheric silicate dust flux was extremely low. After the Eocene, in particular after 20 Ma, Asian dust input has become an isotopically resolvable source, while island arc-derived Pb has remained important to balance the dust input and to produce the observed Pb isotope distribution in the central North Pacific during this period.

[1] Many studies have suggested that continental weathering inputs have controlled the dissolved oceanic budget of hafnium (Hf). However, whether the offset of seawater Nd‐Hf isotope compositions from the terrestrial array can be fully generated by incongruent weathering of continental rocks (the zircon effect) is still not well constrained. In recent years, an increasing amount of combined U‐Pb ages and Hf‐isotopic compositions of riverine detrital zircons have been published. Here a new model of the Nd‐Hf isotopic compositions of the weathered zircon‐free part of the upper continental crust is presented, which is based on published Hf isotope compositions and formation ages of modern riverine detrital zircons combined with Nd isotopic compositions of rocks from the upper continental crust. Our model results indicate that the Nd‐Hf isotopic composition of the weathered zircon‐free part of the upper continental crust is not consistent with the seawater isotopic compositions. This suggests that the elevated seawater Hf isotope compositions for given Nd isotope compositions cannot be fully explained by incongruent zircon weathering of the continents, which is also supported by a recent study demonstrating incongruent weathering of other minerals than zircon.

The northern margin of South China Sea contains several favorable areas for occurrence of gas hydrate. In this study, we collected pore water samples in two piston cores (X-01 and D-01) from Xisha Trough and Dongsha area, respectively, and the concentrations of sulfate and carbon isotopic compositions of dissolved inorganic carbon (DIC) were measured. The results showed different geochemical characteristics in these two sites. The X-01 core shows relatively constant δ13C-DIC values and sulfate concentrations, which suggest that anaerobic methane oxidation (AMO) processes did not occur in this site. In contrast, very large variation in δ13C-DIC values and sulfate concentrations are revealed in D-01 core, and good linear correlations for sulfate gradients and δ13C-DIC values are observed. The calculated sulfate-methane interface (SMI) depth is 9.6 mbsf. These data indicate that an AMO process occurred in sediments with large methane flux from depth in the Dongsha area, which are comparable to other gas hydrate locations in the world oceans such as the Blake Ridge. We suggest that the Dongsha area is one of the most favorable targets for future gas hydrate exploration.

Except for direct drilling and sampling of marine gas hydrates, the occurrence of gas hydrates has been identified generally by inference from indirect evidence, derived from geological, geophysical, and geochemical data. In this paper, we intend to discuss the geochemical anomalies of pore waters and their implications for gas hydrate occurrence in the northern continental slope of the South China Sea. The molecular concentration and isotopic composition of methane in sediments can provide clues to gas sources, whereas ionic and isotopic compositions of pore waters, such as steep SO42- gradients, shallow SMI (sulfate-methane interface) depths; decreasing pore water chlorinity, and heavy oxygen isotopic compositions, are used to identify gas hydrate occurrence and the distribution and thickness of sediment layers containing gas hydrates. Other good geochemical indicators include anions and cations concentrations such as Br-, I-, PO43-, NH4+, Ca2+, Mg2+, Sr2+, B3+, Li+, and Ba2+ in pore waters. We also found that the very negative carbon isotopic compositions of dissolve inorganic carbon (DIC) in pore waters can serve as good indicators for gas hydrate occurrence. In the South China Sea, three most promising target areas for gas hydrates include the Dongsha, Shenhu, and Xisha Trough.

The newly discovered Dapingzhang polymetallic copper deposit in the Lanping-Simao Basin is hosted in volcanic rocks. The orebodies include an upper stratiform and lentiform massive sulfide orebody, and a lower vein type and disseminated sulfide orebody. The Rb-Sr isotopes of quartz fluid-inclusions in the vein type orebody yield an isochron age of 118±12 Ma. Fluid- inclusion analysis shows that the ore-forming fluid is of low to middle salinity (2.0–8.0 wt%NaCl), and of low to middle temperature (90~200°C). The δ34S values of pyrite and chalcopyrite minerals in this deposit concentrate at about 0‰. Our modeling and water/rock ratio calculations using available hydrogen-oxygen isotope data suggests an evolved meteoric water origin for the ore-forming fluids, instead of mixture of seawater and magmatic fluids. The Pb isotope composition indicates radiogenic Pb sources, and suggests Pb from sedimentary rocks and mantle-derived volcanic rocks in the basin both contribute to this deposit. In conclusion, the Dapingzhang deposit shares many similar geochemical characteristics with vein type copper deposits in the Lanping-Simao Basin. These data support the conclusion that the Dapingzhang polymetallic copper deposit is a hydrothermal deposit formed during Yanshanian period, not a massive sulfide deposit of submarine-exhalative-sedimentary origin as proposed by previous researchers.

Ore-forming solutions and the origin of mineralizing material in the Dalucao rare earth deposit were studied by means of H, O, C, and Si isotope analyses. The δ13C of the bastnasite range narrowly from −8.1‰ to−8.0‰, while the δD values range from −89‰ to −79‰. The quartz δ30Si of the orebody is −0.3‰, and the δD and δ180 of the quartz-fluid inclusion range from −87‰ to +6.0‰, respectively. The δD and δ180 values of the fluorite-fluid inclusion in the ore body are −99‰ to −11.6‰, respectively. The study shows that the compositions of hydrogen and oxygen isotopes in oreforming fluid of Dalucao rare earth deposit lie in the region between magmatic water and meteoric water. Therefore the ore-forming fluid was mixed from magmatic and meteoric water. The carbon isotopic features suggest that carbon of the bastnasite was from the mantle, carbon of fluorite-fluid inclusions in the ore body was from a mixture carbon source, and carbon of quartz-fluid inclusions was from the mantle.