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Abstract Understanding the interaction between molybdenum (Mo) and organic matter during microbial sulfate reduction is critical for the use of Mo to reconstruct marine redox conditions throughout Earth's history. However, little is known about Mo isotope fractionation and how it relates to organic matter remineralization during microbial sulfate reduction. Here, we report Mo abundances and isotopic (δ98Mo) compositions for bulk‐rock, non‐lithogenic and sequentially extracted fractions, including carbonate (carb), pyrite, and organic matter (OM), of seep carbonate rocks. Our data indicate that the difference between δ98Mocarb and δ98MoOM (Δ98Mocarb‐OM) displays significant variability in the studied samples, ranging between 0.72 and 1.01‰. Remarkably, the obtained Δ98Mocarb‐OM values indicate correlative trends with stable carbon isotope ratios and bulk abundances of (a) total organic carbon, (b) Mo, and (c) pyrite in seep carbonates, which we interpret as reflecting sustained adsorption of isotopically light Mo onto organic matter during enhanced sulfate reduction. On this basis, we put forward the concept that Δ98Mocarb‐OM of authigenic carbonate rocks can be used as a measure of the intensity of sulfate reduction and for reconstructing past interactions between Mo and organic matter in marine sediments.

Abstract Authigenic molybdenum (Moauth) in marine sediments holds great potential to archive the Mo isotopic composition of seawater and biogeochemical processes. However, the factors that control authigenic Mo isotope (δ98Moauth) distribution patterns remain poorly constrained. Here, we report Mo abundances and δ98Mo compositions for bulk‐rock (bulk) and sequentially extracted fractions—including total authigenic (auth; i.e., non‐lithogenic fraction), carbonate (carb), iron and manganese oxyhydroxides, pyrite (py), and organic fractions (OM)—of authigenic carbonates recovered from various hydrocarbon seep sites in the Gulf of Mexico and the South China Sea. Extracted pyrite fractions exhibit Mo contents varying from 0.1 to 23.4 μg/g and generally dominate the Mo budget of seep carbonate rocks. Our data indicate large ranges of δ98Mobulk and δ98Moauth values relative to NIST 3134 (0.25‰), varying from 1.02 to 1.98‰ (n = 4) and from 0.15 to 3.07‰ (n = 34), respectively. The difference in δ98Mo values between carbonate and pyrite fractions of seep carbonate rocks formed under sulfidic conditions increases with higher Moauth contents, suggesting a control of dissolved hydrogen sulfide concentrations on Mo isotope fractionation during carbonate precipitation. Compared with δ98Moauth and δ98Mopy, δ98Mocarb of seep carbonate rocks formed under sulfidic conditions shows a relatively narrow range with an average of 1.98 ± 0.31‰ (1 SD; n = 10), providing constraints on the δ98Mo composition of seawater in the course of Earth history. Overall, our findings show that the δ98Mo composition of sequentially extracted phases of carbonate‐rich sedimentary rocks can provide insights into seawater‐sediment interactions and biogeochemical pathways of Mo during early diagenesis.

Abstract The accumulation of authigenic carbonate in marine sediments has been regarded as a significant contributor to the carbon cycle over Earth's history. However, accurate quantification of the extent of authigenic carbonate formation in both modern and ancient oceans has been challenging due to limited approaches. Here, we analyzed calcium, magnesium, dissolved inorganic carbon, and alkalinity pore‐water profiles of 153 sites influenced by methane diffusion from the northern South China Sea. By combining these data with published data of diffusive sulfate flux, we found a significant positive correlation between carbonate precipitation rate and sulfate flux in the subseafloor. This correlation can be used to quantify the regional extent of authigenic carbonate formation, representing an advantage over a spatial interpolation approach. We therefore propose that the observed correlation can serve as a new approach for quantifying authigenic carbonate formation in shallow sediments along continental margins for both modern and ancient oceans.

Abiotic methane (CH4) and hydrogen (H2), which are produced during marine serpentinization, provide abundant gas source for hydrate formation on ocean floor. However, previous models of CH4–H2 hydrate formation have generally focused on pure water environments and have not considered the effects of salinity. In this study, the van der Waals–Platteeuw model, which considered the effects of salinity on the chemical potentials of CH4, H2, and H2O, was applied in a marine serpentinization environment. The model uses an empirical formula and the Peng–Robinson equation of state to calculate the Langmuir constants and fugacity values, respectively, of CH4 and H2, and it uses the Pitzer model to calculate the activity coefficients of H2O in the CH4–H2–seawater system. The three-phase equilibrium temperature and pressure predicted by the model for CH4–H2 hydrates in pure water demonstrated good agreement with experimental data. The model was then used to predict the three-phase equilibrium temperature and pressure for CH4–H2 hydrates in a NaCl solutions, for which relevant experimental data are lacking. Thus, this study provides a theoretical basis for gas hydrate research and investigation in areas with marine serpentinization.

Methane (CH4) is a powerful greenhouse gas and its largest reservoir on Earth is held in marine sediments. CH4 in marine sediments is mainly stored in gas-hydrate reservoirs and deep sedimentary strata along continental margins, where large amounts of deep-sourced CH4 ascend to different degrees toward the seafloor. However, the amount of deep-sourced CH4 and its role in subseafloor carbon and sulfur cycling remains poorly constrained. We analyzed sulfate (SO42−) profiles of 157 sites along with previous published 85 sites to determine the regional distribution and amount of SO42− reduction for an area of 1.23 × 105 km2 of the northern South China Sea. Then we compared these obtained results with estimates based on sedimentation rates from the same area. Significantly higher regional SO42− flux estimates based on SO42− profiles (4.26 × 10−3 Tmol a−1), compared to lower estimates based on sedimentation rates (1.23 × 10−3 Tmol a−1), reflect abundant ascending deep-sourced CH4. The difference of the regional SO42− flux estimates (3.03 × 10−3 Tmol a−1) represents the amount of SO42− reduced by CH4 through the anaerobic oxidation of CH4 (AOM). Deep-sourced CH4 contributes 71% to total SO42− consumption in the study area, largely exceeding SO42− consumption by organoclastic sulfate reduction. Our findings substantiate that deep-sourced CH4 governs subseafloor carbon and sulfur cycling to a previously underrated extent, fueling extensive chemosynthesis-based ecosystems along continental slope and rise.

The natural dynamics of fluid flow at methane seeps and increasingly human activities influence the biogeochemistry of the microenvironment and further determine the activity of the chemosynthetic communities within these ecosystems. However, ways to reconstruct short-term fluid flow dynamics and to decipher the influence of scientific exploration at seeps are limited. In this study, we present high-resolution trace elements/Ca ratios (Li/Ca, Mg/Ca, Ti/Ca, Mn/Ca, Co/Ca, Cu/Ca, Zn/Ca, Sr/Ca, Zr/Ca, Mo/Ca, Ba/Ca, Th/Ca and U/Ca ratios) from the shells of two species of chemosymbiotic bivalves (the thiotrophic vesicomyid clam Archivesica marissinica and the methanotrophic mussel Gigantidas haimaensis) from the Haima cold seeps of the South China Sea. We found that the complex distribution patterns of some trace elements (Mg/Ca, Sr/Ca, Mo/Ca and U/Ca ratios) in G. haimaensis are largely controlled by mineral composition or age. The observation of Co/Ca and Ba/Ca ratios in both species indicate strong physiological and environmental control on the incorporation of trace elements during the biomineralization process. Besides, the distribution patterns of other trace elements provide information that can be used to discuss open issues such as the loss of trace elements after death of the bivalves, and the possible influence of human activities such as sediment disturbance. Overall, this study emphasizes the potential for using high-resolution element geochemistry of seep bivalve shells to reveal the physiological and environmental factors that control the growth of bivalves, and to elucidate the potential history of fluid discharge at cold seeps.

After nearly 20 years of exploration, various areas of the seafloor with hydrocarbon seepage have been discovered in the South China Sea (SCS). Through linking subsurface and seafloor biospheres, seeps have become natural laboratories to enhance our knowledge on the processes of hydrocarbon migration and associated hydrocarbon-based ecosystems in the marine environment. This review summarizes the distribution of macrofauna in the active seep areas of the SCS and describes the physiological characteristics of three groups of representative macrofauna (bathymodioline mussels, pliocardiine clams, siboglinid tubeworms). In addition, a comparison is made between the seep macrofauna of the SCS and the Northwest Pacific Ocean. Modes of energy transfer and microbial processes are elucidated by integrating trace element, stable isotope, and lipid biomarker data of macrofaunal soft tissues. Our aims are to provide an overview of the macro-ecology of the SCS seeps and to underscore aspects which desire more research efforts in the future.

The lack of the quantification of deep dissolved methane flux prevents us from accurately understanding hydrate accumulation and distribution at a given geologic setting where vertically upward methane advection dominates the hydrate system. The upward deep methane flux was usually applied as an assumed value in many previous studies. Considering the deep methane flux changes the methane concentration in the pore water and further affects the phase transfer between the gas and aqueous phases depending on the in situ methane concentration, we link gas bubbles distribution to deep dissolved methane flux. Here, we constructed a numerical model to quantify the dissolved methane flux from depth based on the parameters related to gas bubble distribution, including the residual gas saturation in sediments and the free gas zone (FGZ) thickness. We then applied our model to ODP Site 995 at the Blake Ridge where methane was sourced from deep layers. Our model results predict an upward deep methane flux of 0.0231 mol/m2/a and the occurrence of another gas interval in deeper sediments, which are consistent with seismic data. We further explored the influence of upward methane flux on hydrate accumulation and found that the thin hydrate occurrence zone at nearby Site 994 likely resulted from a small deep methane flux. Combined with the previous conclusion of high deep methane flux at Site 997, we showed that along the Blake Ridge drilling transect the estimated deep methane fluxes decrease with increasing distance from the crest of the ridge. This approach for quantifying deep methane flux is complementary to the current hydrate accumulation model and provides new insights into the regional methane flux estimation at the Blake Ridge.

The magnesium (Mg) isotopic composition of marine authigenic carbonates is considered as promising archive of ancient seawater geochemistry and paleoenvironments. Previous experimental and theoretical work has shown that Mg isotope fractionation during carbonate mineral formation is a function of mineralogy and precipitation rate. However, information on Mg isotope fractionation is limited for well-defined precipitation rates in natural settings. Here, we investigate pore waters from sediments of an area of active methane seepage in the South China Sea. Low δ13C values (< −48.3‰ VPDB) of dissolved inorganic carbon (DIC) near the sulfate-methane transition zone (SMTZ) indicate that sulfate-driven anaerobic oxidation of methane (SD-AOM) is the predominant biogeochemical process. Pore water composition of dissolved Mg, calcium (Ca), and strontium (Sr) agrees with aragonite as the dominant carbonate mineral at the site ROV1, and high Mg-calcite at sites ROV2 and ROV4. Calculated carbonate precipitation rates are 0.92 μmol cm−2 yr−1 for site ROV2 and 1.24 μmol cm−2 yr−1 for site ROV4; these estimates are similar to previous calculations for seeps from other areas. The pore water δ26Mg values (−0.88‰ to −0.71‰) obtained for the three study sites are similar to those of seawater, in accord with a minor effect of Rayleigh fractionation due to abundant supply of Mg from seawater and insignificant consumption of Mg during carbonate precipitation. The modeled Mg isotope fractionation (ϵ = −2.0‰ to −1.0‰ for core ROV2; ϵ = −1.3‰ to −0.3‰ for core ROV4) can be explained by kinetic isotope fractionation during carbonate precipitation. The calculated carbonate precipitation rates and the degree of fractionation of Mg isotopes support the notion that fractionation is small at high precipitation rates. However, the carbonate precipitation rates calculated for the studied seep environments are much smaller than those in laboratory experiments, documenting a discrepancy of isotopic fractionation between carbonate authigenesis in laboratory experiments and natural environments. These results, including the modeled precipitation rates, provide new constraints for Mg isotope fractionation in natural settings.

Cold seeps where methane-rich fluids escape from the seafloor generally support enormous biomass of chemosynthetic organisms and associated fauna. In addition to transporting a great amount of methane toward the seafloor, cold seeps also contribute to the aged, dissolved organic carbon (DOC) pool in the deep ocean. Here, two sediment cores from the “Haima cold seeps,” northern South China Sea and a nearby reference core were analyzed for pore-water sulfate and DOC concentrations, δ13C of DOC, and optical properties of dissolved organic matter (DOM). High DOC concentrations (0.9–3.7 mM) accompanied by extremely low δ13C values (−43.9 to −76.2‰) suggest the conversion of methane into sedimentary DOC pool in the seep sediments. Parallel factor analysis (PARAFAC) of the fluorescence excitation-emission matrices shows higher fluorescent intensities of labile protein-like components (C2 and C4) and lower fluorescent intensities of refractory humic-like components (C1 and C3) in the seep cores compared to the reference core. The intensity of C2 is positively correlated with DOC concentrations and δ13C-DOC in the seep sediments, suggesting that the labile protein-like DOM was produced by the anaerobic oxidation of methane (AOM). Moreover, low humification index (HIX) and high biological index (BIX) values also indicate intensified production of relatively labile DOM with lower degradation degree in the seep cores compared to the reference core. Hence, we highlight that methane-derived DOC may serve as important carbon and energy sources for heterotrophic microbial communities due to its relatively labile nature.

Methane seeps are chemosynthetic ecosystems in the deep-sea environment. Microbial community structures have been extensively studied in the seepage-affected sediments and investigation in the water column above the seeping sites is still lacking. In this study, prokaryotic communities in the bottom water about 50 cm from the seabed at methane seeps with various seepage intensities in Haima, South China Sea were comparatively studied by using 16S ribosomal RNA gene sequencing. These sites were assigned based on their distinct methane content levels and seafloor landscapes as the non-seepage (NS) site, low-intensity seepage (LIS) site, and high-intensity seepage (HIS) site. The abundances of the dominant phyla Proteobacteria, Bacteroidetes, and Actinobacteria differed significantly between NS and the two seepage sites (p < 0.05). Alpha diversity differed among the three sites with the HIS site showing the lowest community diversity. Principal component analysis revealed highly divergent bacterial community structures at three sites. Many environmental variables including temperature, alkalinity, pH, methane, dissolved organic carbon (DOC), and inorganic nutrients were measured. Redundancy analysis indicated that methane content is the key environmental factor driving bacterial community variation (p = 0.001). Linear discriminant analysis effect size analysis identified various differentially enriched genera at the LIS and HIS sites. Phylogenetic analysis revealed close phylogenetic relationship among the operational taxonomic units of these genera with known oil-degrading species, indicating oil seepage may occur at the Haima cold seeps. Co-occurrence networks indicated that the strength of microbial interactions was weakest at the HIS site. This study represents a comprehensive comparison of microbial profiles in the water column of cold seeps in the SCS, revealing that the seepage intensity has a strong impact on bacterial community dynamics.

By employing a specific particle interaction theory and a high-precision equation of states for the liquid and vapor phases of H2, respectively, a new H2 solubility model in pure water and aqueous NaCl solutions is proposed in this study. The model established by fitting the experimental data of H2 solubility can be used to estimate H2 solubility in pure water at temperatures and pressures of 273.15–423.15 K and 0–1100 bar, respectively, and in salt solutions (NaCl concentration = 0–5 mol/kg) at temperatures and pressures of 273.15–373.15 K and 0–230 bar, respectively. By adopting the theory of liquid electrolyte solutions, the model can also be used to predict H2 solubility in seawater without fitting the experimental data of a seawater system. Within or close to experimental data uncertainty, the mean absolute percentage error between the model-predicted and experimentally obtained H2 solubilities was less than 1.14%.

The surface sediments collected from the southern Mariana Trench at water depths between ca. 4900 m and 7068 m were studied using lipid biomarker analyses to reveal the origin and distribution of organic matters. For all samples, an unresolved complex mixture (UCM) was present in the hydrocarbon fractions, wherein resistant component tricyclic terpanes were detected but C27–C29 regular steranes and hopanes indicative of a higher molecular weight range of petroleum were almost absent. This biomarker distribution patterns suggested that the UCM and tricyclic terpanes may be introduced by contamination of diesel fuels or shipping activities and oil seepage elsewhere. The well-developed faults and strike-slip faults in the Mariana subduction zone may serve as passages for the petroleum hydrocarbons. In addition, the relative high contents of even n-alkanes and low Carbon Preference Indices indicated that the n-alkanes were mainly derived from bacteria or algae. For GDGTs, the predominance of GDGT-0 and crenarchaeol, together with low GDGT-0/Crenarchaeol ratios (ranging from 0.86 to 1.64), suggests that the GDGTs in samples from the southern Mariana Trench were mainly derived from planktic Thaumarchaeota. However, the high GDGT-0/crenarchaeol ratio (10.5) in sample BC07 suggests that the GDGTs probably were introduced by methanogens in a more anoxic environment. Furthermore, the n-alkanes C19–C22 and the n-fatty acids C20:0–C22:0 were depleted in 13C by 3‰ compared to n-alkanes C16–C18 and the n-fatty acids C14:0–C18:0, respectively, which was interpreted to result from the preferential reaction of fatty acid fragments with carbon “lighter” terminal carboxyl groups during carbon chain elongation from the precursors to products. The abundance of total alkanes, carboxylic acids, alcohols and total lipids were generally increased along the down-going seaward plate, suggesting the lateral organic matter inputs play an important role in organic matter accumulation in hadal trenches. The extremely high contents of biomarkers in sample BC11 were most likely related to trench topography and current dynamics, since the lower steepness caused by graben texture and proximity to the trench axis may result in higher sedimentation rate. This paper, for the first time, showed the biomarker patterns in surface sediments of the Mariana Trench and shed light on biogeochemistry of the hardly reached trench environment. Keywords: Mariana Trench, Lipid biomarkers, Organic matter, Topography, Hydrodynamics

Methane (CH4), the most abundant hydrocarbon gas in the atmosphere, plays an important role in global climate change. Quantifying the dissolved methane and its air-sea flux from hydrocarbon seeps is therefore of great importance. Large quantities of natural gas are emitted from the seafloor to the coastal ocean near the Lingtou Promontory, South China Sea. We quantified concentrations of methane in surface and bottom waters at 48 stations in a 56 km2 study area. High spatial variability in dissolved methane concentrations was observed in the surface mixed layer (0.5 m water depth) and bottom water (water-sediment interface), with values ranging from 2.90 nmol L−1 to 13570.02 nmol L−1 and from 4.98 nmol L−1 to 31740.02 nmol L−1, respectively. The significant difference between concentrations of dissolved methane in surface and bottom waters suggests that most of the methane emitted from the seafloor is dissolved in the water column. The dissolution of methane in seawater may result in local oxygen depletion that may lead to ecological effects. The δ13C values of dissolved methane ranging from −59.76‰ to −48.59‰ indicate a mixture of biogenic and thermogenic gas sources. The average air-sea methane flux of Yinggehai Basin was 672.57 μmol m−2 d−1, which cannot be ignored in environment assessment. Coastal regions, especially with hydrocarbon seeps in shallow waters of the continental margin, may therefore be an important source of methane to the atmosphere.

Gas hydrates, acting as a dynamic methane reservoir, store methane in the form of a solid phase under high-pressure and low-temperature conditions and release methane through the sediment column into seawater when they are decomposed. The seepage of methane-rich fluid (i.e., cold hydrocarbon seeps) fuels the chemosynthetic biota-inhabited surface sediments and represents the major pathway to transfer carbon from sediments to the water column. Generally, the major biogeochemical reactions related to carbon cycling in the anoxic marine sediments include organic matter degradation via sulfate reduction (OSR), anaerobic oxidation of methane (AOM), methanogenesis (ME), and carbonate precipitation (CP). In order to better understand the carbon turnover in the cold seeps and gas hydrate-bearing areas of the northern South China Sea (SCS), we collected geochemical data of 358 cores from published literatures and retrieved 37 cores and corresponding pore water samples from three areas of interest (i.e., Xisha, Dongsha, and Shenhu areas). Reaction-transport simulations indicate that the rates of organic matter degradation and carbonate precipitation are comparable in the three areas, while the rates of AOM vary over several orders of magnitude (AOM: 8.3-37.5 mmol·m-2·yr-1 in Dongsha, AOM: 12.4-170.6 mmol·m-2·yr-1 in Xisha, and AOM: 9.4-30.5 mmol·m-2·yr-1 in Shenhu). Both the arithmetical mean and interpolation mean of the biogeochemical processes were calculated in each area. Averaging these two mean values suggested that the rates of organic matter degradation in Dongsha (25.7 mmol·m-2·yr-1) and Xisha (25.1 mmol·m-2·yr-1) are higher than that in Shenhu (12 mmol·m-2·yr-1) and the AOM rate in Xisha (135.2 mmol·m-2·yr-1) is greater than those in Dongsha (27.8 mmol·m-2·yr-1) and Shenhu (17.5 mmol·m-2·yr-1). In addition, the rate of carbonate precipitation (32.3 mmol·m-2·yr-1) in Xisha is far higher than those of the other two regions (5.3 mmol·m-2·yr-1 in Dongsha, 5.8 mmol·m-2·yr-1 in Shenhu) due to intense AOM sustained by gas dissolution. In comparison with other cold seeps around the world, the biogeochemical rates in the northern SCS are generally lower than those in active continental margins and special environments (e.g., the Black sea) but are comparable with those in passive continental margins. Collectively, ~2.8 Gmol organic matter was buried and at least ~0.82 Gmol dissolved organic and inorganic carbon was diffused out of sediments annually. This may, to some extent, have an impact on the long-term deep ocean carbon cycle in the northern SCS.

A remarkable exposure of tubular authigenic carbonates was found on the seafloor in the Dongsha area of the South China Sea (SCS). The tubular carbonates, around 2–3 cm in diameter and usually less than 10 cm in length, represent broken fragments of once-larger pipes that now protrude from muddy sediments. The morphology, carbon and oxygen stable isotope compositions, and trace and rare earth element contents of the carbonates were analyzed to decipher the mode of carbonate formation. The tubular carbonates exhibit a dark brown coating of iron and manganese hydrous oxides, indicating prolonged exposure to oxic bottom waters. The carbonate content of the micritic pipes falls between 12.5 and 67.3 wt.% with an average of 42.0 wt.%, suggesting formation within the sediment. This inference is supported by trace and rare earth element patterns including a moderate enrichment of middle rare earth elements. Low δ13C values (as low as −50.3‰, Vienna Pee Dee Belemnite (VPDB)) suggest that carbonate precipitation was induced by the anaerobic oxidation of methane. The unusually positive δ18O values of the carbonates (as high as +5.3‰, VPDB) are believed to reflect the destabilization of locally abundant gas hydrate. Taken together, it is suggested that pipe formation was initiated by sediment-dwelling organisms, such as crustaceans or bivalves. The burrows subsequently acted as conduits for upward fluid migration. The lithification of the sediment directly surrounding the conduits and the partial filling of the conduits with carbonate cement resulted in the formation of tubular carbonates. Turbidity currents, sediment slumps, or the vigorous emission of fluids probably induced the fragmentation of tubular carbonates within the sediment. The carbonate fragments had been further subjected to winnowing by bottom currents. This study provides insight into the interaction of megafauna burrowing with fluid migration and carbonate formation at hydrocarbon seeps, highlighting the role of bottom currents and mass wasting on the formation of fragmented tubular carbonates.

Widespread cold seeps along continental margins are significant sources of dissolved carbon to the ocean water. However, little is known about the methane turnovers and possible impact of seepage on the bottom seawater at the cold seeps in the South China Sea (SCS). We present seafloor observation and porewater data of six push cores, one piston core and three boreholes as well as fifteen bottom-water samples collected from four cold seep areas in the northwestern SCS. The depths of the sulfate−methane transition zone (SMTZ) are generally shallow, ranging from ~7 to −2 yr−1. The δ13C and Δ14C values of bottom-water dissolved inorganic carbon (DIC) suggest discharge of 13C- and 14C-depleted fossil carbon to the bottom water at the cold seep areas. Based on a two-endmember estimate, cold seeps fluids likely contribute 16−26% of the bottom seawater DIC and may have an impact on the long-term deep-sea carbon cycle. Our results reveal the methane-related carbon inventories are highly heterogeneous in the cold seep systems, which are probably dependent on the distances of the sampling sites to the seepage center. To our knowledge, this is the first quantitative study on the contribution of cold seep fluids to the bottom-water carbon reservoir of the SCS, and might help to understand the dynamics and the environmental impact of hydrocarbon seep in the SCS.

High-magnesium calcite (HMC) and aragonite are metastable minerals, which tend to convert into low-magnesium calcite (LMC) and dolomite. During this process, primary compositions are frequently altered, resulting in the loss of information regarding the formation environment and the nature of fluids from which the minerals precipitated. Petrological characteristics have been used to recognize primary LMC, however, neither the element distribution within primary LMC nor the effect of diagenetic alteration on element composition have been studied in detail. Here, two mostly authigenic carbonate lithologies from the northern Gulf of Mexico dominated by primary LMC were investigated to distinguish element compositions of primary LMC from LMC resulting from diagenetic alteration. Primary LMC reveals similar or lower Sr/Ca ratios than primary HMC. The lack of covariation between Sr/Ca ratios and Mg/Ca ratios in the studied primary LMCs are unlike compositions observed for LMC resulting from diagenetic alteration. The Sr/Mn ratios and Mn contents of the primary LMCs are negatively correlated, similar to secondary, diagenetic LMC. Element mapping for Sr and Mg in the primary LMC lithologies revealed no evidence of conversion from aragonite or HMC to LMC, and a homogenous distribution of Mn is in accordance with the absence of late diagenetic alteration. Our results confirm that Sr/Ca ratios, Mg/Ca ratios, and element systematics of primary LMC are indeed distinguishable from diagenetically altered carbonates, enabling the utilization of element geochemistry in recognizing primary signals in carbonate archives.

Natural cold seeps are an important source of methane and other greenhouse gases to the ocean and atmosphere in the marine environment. Accurate quantification of methane bubble fluxes from cold seeps is vital for evaluating their influence on the global methane budget and climate change. We quantified the flux of gas bubbles released from two natural cold seep sites in the South China Sea: one seep vent in the Haima cold seeps (1400 m depth) and three seep vents at Site F (1200 m depth). We determined bubble diameter, size distribution, and bubble release rate using image processing techniques and a semiautomatic bubble-counting algorithm. The bubble size distributions fit well to log-normal distribution, with median bubble diameters between 2.54 mm and 6.17 mm. The average bubble diameters and release rates (4.8−26.1 bubbles s−1) in Site F was lower than that in Haima cold seeps (22.6 bubbles s−1), which may be attributed to a variety of factors such as the nature of the gas reservoir, hydrostatic pressure, migration pathways in the sediments, and pore size. The methane fluxes emitted at Haima cold seeps (12.6 L h−1) and at Site F (4.9 L h−1) indicate that the Haima and Site F cold seeps in the South China Sea may be a source of methane to the ocean. However, temporal variations in the bubble release rate and the geochemical characteristics of the seeps were not constrained in this study due to the short observational time interval.

Deep-water pockmarks are frequently accompanied by the occurrence of massive gas hydrates in shallow sediments. A decline in pore-water Cl− concentration and rise in δ18O value provide compelling evidence for the gas hydrate dissociation. Mega-pockmarks are widely scattered in the southwestern Xisha Uplift, northern South China Sea (SCS). Pore water collected from a gravity-core inside of a mega-pockmark exhibits a downward Cl− concentration decrease concomitant with an increase in δ18O value at the interval of 5.7–6.7 mbsf. Concentrations of Cl−, Na+, and K+ mainly cluster along the seawater freshening line without distinct Na+ enrichment and K+ depletion. Thus, we infer that the pore water anomalies of Cl− concentrations and δ18O values are attributed to gas hydrate dissociation instead of clay mineral dehydration. Moreover, the lower δ18O values of sulfate in the target core (C14) than those in the reference core (C9) may be associated with the equilibrium oxygen fractionation during sulfate reduction between sulfate and the relatively 18O-depleted ambient water resulting from gas hydrate formation. The gas hydrate contents are estimated to be 6%–10% and 7%–15%, respectively, according to the offset of Cl− concentrations and δ18O values from the baselines. This pockmark field in southwestern Xisha Uplift is likely to be a good prospective area for the occurrence of gas hydrate in shallow sediments.

Authigenic low-magnesium calcite (LMC)—a mineral phase that should precipitate in calcite seas rather than today’s aragonite sea—was recently discovered at the seafloor of the Gulf of Mexico (GoM) at water depths of 65 m (site SS296) and 189 m (site GC53). This study investigates the mineralogical, petrographic, and geochemical characteristics of LMC from both sites to reveal its formation process. The δ18O values of LMC from site SS296 cluster in two groups (−0.6‰ to 1.7‰; 6.3‰ to 7.5‰) and the presence of cone-in-cone texture in the samples with lower δ18O values suggest precipitation at higher temperatures and greater depth. Low δ18O values of LMC from site GC53 ranging from −9.4‰ to −2.5‰ indicate an influence of meteoric waters during formation. LMC at both sites reveals a wide range of δ13C values (−17.4‰ to 2.6‰), indicating various carbon sources including seawater and/or organic matter. This interpretation is further supported by the δ13C values of organic carbon extracted from the LMC lithologies (δ13Corg: from −26.8‰ to −18.9‰). Relatively low Sr concentrations of LMC samples regardless of variable 87Sr/86Sr ratios, ranging from 0.707900 to 0.708498 for site GC53 and from 0.709537 to 0.710537 for site SS396, suggest the exchange of Sr between pore fluids and ambient sediments/rocks. The observed wide range of 87Sr/86Sr ratios and the enrichment of Fe and Mn in LMC is in accordance with pore fluids deriving from the dissolution of Louann salt. Overall, this study reveals that the formation of LMC at sites SS296 and GC53 was favored by the presence of low Mg/Ca ratio pore fluids resulting from salt dissolution in subsurface environments when sufficient dissolved inorganic carbon was available. These results are essential for understanding the formation of marine LMC at times of an aragonite sea, highlighting the role of formation environments—open environments close to or at the seafloor vs. confined subseafloor environments typified by pore waters with a composition largely different from that of seawater.

Natural hydrocarbon seeps in marine environment are important sources of methane and other greenhouse gases into the ocean and the atmosphere. This greenhouse gas seepage influences the global methane budget and global climate change. Hydrocarbon seeps on the shallow seabed produce a near-shore gas bubble zone along the western coast of Hainan Island, in the northern South China Sea. However, few studies on the quantitative value of the methane flux and on temporal variation and influence factors of hydrocarbon seeps have been conducted until now. This study describes the results of continuous gas vent measurements for 420 hours on the seabed of the Lingtou promontory shore. The amount of gas released from a single gas vent was 30.5 m3 during the measurement period. The gas flow rate ranged from 22 - 72 L h-1, with an average rate of 53.4 L h-1. The time series analyses of the 420-hour record clearly show three principal tidal components with periods of 5.4, 4.6, and 2.4 hours, which are the main factors controlling the gas flow rate. Low flow rates were associated with high tide and high flow rates associated with low tide. A 1-m increase in seawater height results in a decrease of 20 - 30 L h-1 or 35 - 56% of the hourly flow rate. Therefore, the changes in gas volume escape from the pore could be attributed to the hydrostatic pressure effect induced by water depth. This dominant mechanism controlled pore activation as well as the gas flow rate, suggesting that in the marine environment, especially the shallow-water shelf area, sea level changes may result in great variations in methane release into the ocean and atmosphere.