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Carbon sphere@layered double hydroxides filled cellulose nanofibers (ACS@LDHs/CNF) aerogel was successfully synthesized. The removal rate of Cr(VI) using ACS@LDHs/CNFs aerogel at a solid-liquid ratio of 1 g/L was 89.4%, which was higher compared to the removal rate of 65.2% using LDHs alone. The adsorption capacity of ACS@LDHs/CNFs for Cr(VI) was determined to be 44.9 mg/g. The adsorption kinetics followed the pseudo-second-order kinetic equation, and the isotherm data showed good agreement with the Langmuir model. The adsorption mechanism of Cr(VI) onto ACS@LDHs/CNFs aerogel was also investigated. Additionally, the ACS@LDHs/CNFs aerogel demonstrated consistent high adsorption efficiency over 4 consecutive cycles of adsorption-regeneration. [ABSTRACT FROM AUTHOR]

Flexible polyurethane foam (FPUF) coated with nanocarbon black (nano-CB), alginate and polyethylenemine was prepared by layer-by-layer self-assembly method. The successful synthesis of the target coated PU foams was demonstrated by comparing untreated and treated FPUFs. TGA results showed that the nano-CB could retard the thermal decomposition of treated FPUFs and improve the char residues of FPUF composites at high temperature. In the cone test, the peak heat release rate, peak smoke production rate and total smoke production of the PU-3 (with 17.6 wt% weight-gain) were shown to be reduced by 47.7%, 41.8% and 81.5% as compared with untreated FPUF, respectively. [ABSTRACT FROM AUTHOR]

A flame retardant and hydrophobic coating was prepared by layer-by-layer self-assembly on cotton fabric. The coated fabric was treated with polyethylenimine, hypophosphorous acid modified chitosan, sepiolite and poly(dimethylsiloxane) (PDMS). The thermal stabilities of treated cotton fabrics were enhanced at high temperature compared with those of untreated cotton fabrics. The cotton fabric treated with sepiolite (cotton-3) and cotton fabric treated with sepiolite and PDMS (cotton-4) showed 50.2% and 56.1% reductions in the peak heat release rate (PHRR) values compared with those of untreated cotton. Moreover, the sepiolite and PDMS in the coating resulted in hydrophobic surfaces on the cotton fabrics. [ABSTRACT FROM AUTHOR]

The archaeal phylum Bathyarchaeota, which is composed of a large number of diverse lineages, is widespread and abundant in marine sediments. Environmental factors that control the distribution, abundance and evolution of this largely diversified archaeal phylum are currently unclear. In this study, a new pair of specific primers that target the major marine subgroups of bathyarchaeotal 16S rRNA genes was designed and evaluated to investigate the distribution and abundance of Bathyarchaeota in marine sediments. The abundance of Bathyarchaeota along two sediment cores from the deep-sea sediments of South China Sea (SCS, each from the Dongsha and Shenhu area) was determined. A strong correlation was found between the bathyarchaeotal abundance and the content of total organic carbon (TOC), suggesting an important role of Bathyarchaeota in organic matter remineralisation in the sediments of SCS. Furthermore, diversity analysis revealed that subgroups Bathy-2, Bathy-8 and Bathy-10 were dominant bathyarchaeotal members of the deep-sea sediments in the SCS. Bathy-8 was found predominantly within the reducing and deeper sediment layers, while Bathy-10 occurred preferentially in the oxidizing and shallower sediment layers. Our study lays a foundation for the further understanding of the ecological functions and niche differentiation of the important but not well-understood sedimentary archaeal group. [ABSTRACT FROM AUTHOR]

Authigenic carbonates recovered from two newly discovered active cold seeps on the northwestern slope of the South China Sea have been studied using petrography, mineralogy, stable carbon and oxygen isotopic, as well as trace element compositions, together with AMS 14 C ages of shells of seep-dwelling bivalves to unravel fluid sources, formation conditions, and seepage dynamics. The two seeps (ROV1 and ROV2), referred to as ‘Haima seeps’ herein, are approximately 7 kilometers apart, and are typified by abundant carbonate rocks represented bycrusts and nodules. Aragonite and high-Mg calcite are the main carbonate minerals. Based on low δ 13 C carbonate values ranging from −43.0‰ to −27.5‰ (V-PDB) methane is apparently the predominant carbon source of seep carbonates. The corresponding δ 18 O values, varying from 2.5‰ to 5.8‰ (V-PDB), mostly are higher than calculated values representing precipitation in equilibrium with seawater (2.5‰ to 3.8‰), which probably reflects past destabilization of locally abundant gas hydrates. In addition, we found that carbonates with bivalve shells are generally aragonite-dominated, and bear no barium enrichment but uranium enrichments, reflecting shallow formation depths close to the seafloor. In contrast, carbonate crusts without bivalve shells and nodules contain more calcite, and are characterized by major molybdenum enrichment and different degrees of barium enrichment, agreeing with precipitation at greater depth under strictly anoxic conditions. AMS 14 C ages suggest that a major episode of carbonate precipitation occurred between 6.1 ka and 5.1 ka BP at the Haima seeps, followed by a possibly subordinate episode from approximately 3.9 ka to 2.9 ka BP. The common occurrence of dead bivalves at both sites indicates that chemosynthesis-based communities flourished to a greater extent in the past, probably reflecting a decline of seepage activity in recent times. Overall, these results confirm that authigenic carbonates from gas hydrate-bearing areas can provide insight into long-term seepage dynamics and the genesis and fate of marine gas hydrate reservoirs. [ABSTRACT FROM AUTHOR]

Research on the origin and source of hydrate-bound gas and its relationship to deep conventional oil and gas accumulation in a basin is critical to understanding the accumulation mechanism of gas hydrates and to resource evaluation of gas hydrate accumulation. In this study, the hydrate-bound gas obtained via pressure coring and the production gas recovered during a production test on a gas hydrate reservoir in the Shenhu area offshore of Southern China were tested and discussed. The geochemical analysis results indicate that methane is the predominant gas, and heavier hydrocarbons (C2+) are also present but in low concentrations. The molecular compositions of the hydrate gas recovered from two production test sites are similar to those of the hydrate-bound gas acquired via pressure coring. In addition to the isotopic composition of the methane, the carbon and hydrogen isotopes of the C2+ hydrocarbons were obtained for the first time. The δ13C isotopes of the methane range from −66.6‰ to −46.2‰, indicating that the hydrate-bound gases have a mixed origin, containing both biogenic and thermogenic gases. The plot of δ13C 1 versus δ13C 2 suggests that the biogenic and thermogenic hydrocarbons were derived from marine organic matter and terrestrial organic matter, respectively. The isotopic characterization of the hydrate-bound gas reveals that the thermogenic hydrate gas contains both humic-type gas and sapropel-type gas, but the sapropel-type gas is predominant. The source rocks of the thermogenic hydrate gas are interpreted to be both the gas-prone coal measure strata of the Enping Formation and the oil-prone medium-deep lacustrine strata of the Wenchang Formation, the latter of which contributed more to the hydrocarbon supply of the gas hydrates. In addition, the maturity of the source rocks of the thermogenic hydrate gas may be lower than that of the deeply buried conventional hydrocarbons discovered in the Baiyun Sag-Panyu Low Uplift area. The seismic profile crossing the shallow gas hydrate accumulations and deep conventional gas reservoirs clearly shows that the proven LW3-1 thermogenic gas reservoir communicated with the gas hydrate stability zone through vertical migration pathways formed by high-angle faults and gas chimneys. This indicates that there was a cogenetic relationship between the thermogenic hydrate gas and the deep conventional hydrocarbon reservoir, which was supplied the thermogenic gas derived from both the Wenchang and Enping formations. The major implications of this finding are that it confirms, rather than theorizes, the identity of the hydrocarbon source rocks of the thermogenic hydrate gas in the Shenhu area for the first time, and it demonstrates the coupling relationship between the shallow gas hydrate accumulations and the deep conventional reservoirs proposed in previous studies. The mechanisms of hydrocarbon migration and gas hydrate accumulation in the production test gas hydrate reservoirs in the Shenhu area were also identified, providing a valuable reference for subsequent exploration and for the potential exploitation of gas hydrate reservoirs in the South China Sea. • The δ13C and δD isotopes of the heavier hydrocarbons (C2+) in the Shenhu area are obtained for the first time. • The origin of the hydrate gas obtained from the second trial production well in the Shenhu area is confirmed. • The hydrocarbon source rocks of the thermogenic hydrate gas in the Shenhu area are identified. • Coupled paragenetic relationship between shallow gas hydrate and deep petroleum system is revealed. [ABSTRACT FROM AUTHOR]

Abstract: In this study, a simple solvent dilution followed by highly selective and sensitive gas chromatography–triple quadrupole mass spectrometry (GC–MS–MS) detection was employed to quantify diamondoids in crude oils. Runtime parameters, i.e., parent and daughter ions, collision energy (CE) and scan time, were optimized to obtain maximum selectivity and sensitivity for target analytes. Under optimum conditions, the reproducibility and accuracy of the method were tested and found to be satisfactory. Comparison of GC–MS–MS and GC–MS methods for the determination of diamondoids indicates that GC–MS–MS yields higher sensitivity (method quantitation limits of 0.08–0.37μg/goil) and better selectivity than GC–MS (method quantitation limits of 0.78–8.44μg/goil) due to the elimination of matrix ion interferences using the selected reaction monitoring (SRM) mode. In addition, quantitative data confirm that group separation has a considerable effect on the quantification of diamondoids and the effect appears to depend on multiple factors. Two crude oils (TZ261 and TD2) from the Tarim Basin, China were used to evaluate the GC–MS–MS method. The results prove that the GC–MS–MS method is a promising tool for quantitative analysis of diamondoids in crude oils, especially for oil samples with low diamondoid concentrations. [Copyright &y& Elsevier]

• The gas production from hydrate dissociation accounting for about 85%. • Analysis of the radius of the hydrate dissociation area in this production test. • Five-year prediction of long-term influence radius of pressure drop. • Exploration of favorable areas for the formation of secondary hydrates. • Analysis of the response of pressure and temperature of hydrate reservoirs. The first offshore natural gas hydrate production test of China in 2017 has proved the feasibility of hydrate exploitation from clayey-silt reservoirs, which possesses the highest reservoirs than other types of hydrate resources. However, owing to the absence of monitoring wells in this production test, the hydrate dissociation behavior cannot be analyzed through pressure and temperature changes of hydrate reservoirs. This paper focuses on the simulation study on the detailed response of the temperature and pore pressure of hydrate reservoirs of Well SHSC-4 during the gas production by depressurization. Meanwhile, it highlights the analysis of favorable areas for the formation of secondary hydrates and the influence of the secondary hydrates on pressure and temperature field of hydrate reservoirs. The simulation results indicate that in the first 60 days, the hydrate reservoirs feature a dissociation radius of about 5 m, and the gas production from hydrate dissociation accounts for about 85%. After 1 year, 2 years and 5 years of hydrate exploitation, the influence radius of low-pressure area (<10 MPa) is 15 m, 16 m and 17 m, respectively, suggesting that the hydrate reservoirs have higher gas production efficiency in the first year. Furthermore, the temperature and pressure of hydrate reservoirs are not favorable to the formation of secondary hydrates in the first 60 days. In long-term production, secondary hydrates are mainly formed at hydrate dissociation front. This can increase the pore pressure and further decrease the effective stress in the local areas of hydrate reservoirs, thus affecting mechanical stability of the local hydrate reservoirs. [ABSTRACT FROM AUTHOR]

Studying deep-water cold seep systems is of great significance to gas hydrate exploration due to their close relationship. Various cold seep systems and related gas hydrate accumulations have been discovered in the northern South China Sea in the past three decades. Based on high-resolution seismic data, subbottom profiles, in situ submergence observations, deep drilling and coring, and hydrate gas geochemical analyses, the geological and geophysical characteristics of these cold seep systems and their associated gas hydrate accumulations in the Qiongdongnan Basin, the Shenhu area, the Dongsha area, and the Taixinan Basin have been investigated. Cold seep systems are present in diverse stages of evolution and exhibit various seabed microgeomorphic, geological, and geochemical features. Active cold seep systems with a large amount of gas leakage, gas plumes, and microbial communities and inactive cold seep systems with authigenic carbonate pavements are related to the variable intensity of the gas-bearing fluid, which is usually derived from the deep strata through mud diapirs, mud volcanoes, gas chimneys, and faults. Gas hydrates are usually precipitated in cold seep vents and deeper vertical fluid migration pathways, indicating that deep gas-bearing fluid activities control the formation and accumulation of gas hydrates. The hydrocarbons collected from cold seep systems and their associated gas hydrate reservoirs are generally mixtures of biogenic gas and thermogenic gas, the origin of which is generally consistent with that of deep conventional gas. We also discuss the paragenetic relationship between the gas-bearing fluid and the seafloor morphology of cold seeps and the deep-shallow coupling of gas hydrates, cold seeps, and deep petroleum reservoirs. It is reasonable to conclude that the deep petroleum systems and gas-bearing fluid activity jointly control the development of cold seep systems and the accumulation of gas hydrates in the northern South China Sea. Therefore, the favorable areas for conventional oil and gas enrichment are also prospective areas for exploring active cold seeps and gas hydrates. [ABSTRACT FROM AUTHOR]

Studying deep-water cold seep systems is of great significance to gas hydrate exploration due to their close relationship. Various cold seep systems and related gas hydrate accumulations have been discovered in the northern South China Sea in the past three decades. Based on high-resolution seismic data, subbottom profiles, in situ submergence observations, deep drilling and coring, and hydrate gas geochemical analyses, the geological and geophysical characteristics of these cold seep systems and their associated gas hydrate accumulations in the Qiongdongnan Basin, the Shenhu area, the Dongsha area, and the Taixinan Basin have been investigated. Cold seep systems are present in diverse stages of evolution and exhibit various seabed microgeomorphic, geological, and geochemical features. Active cold seep systems with a large amount of gas leakage, gas plumes, and microbial communities and inactive cold seep systems with authigenic carbonate pavements are related to the variable intensity of the gas-bearing fluid, which is usually derived from the deep strata through mud diapirs, mud volcanoes, gas chimneys, and faults. Gas hydrates are usually precipitated in cold seep vents and deeper vertical fluid migration pathways, indicating that deep gas-bearing fluid activities control the formation and accumulation of gas hydrates. The hydrocarbons collected from cold seep systems and their associated gas hydrate reservoirs are generally mixtures of biogenic gas and thermogenic gas, the origin of which is generally consistent with that of deep conventional gas. We also discuss the paragenetic relationship between the gas-bearing fluid and the seafloor morphology of cold seeps and the deep-shallow coupling of gas hydrates, cold seeps, and deep petroleum reservoirs. It is reasonable to conclude that the deep petroleum systems and gas-bearing fluid activity jointly control the development of cold seep systems and the accumulation of gas hydrates in the northern South China Sea. Therefore, the favorable areas for conventional oil and gas enrichment are also prospective areas for exploring active cold seeps and gas hydrates. [ABSTRACT FROM AUTHOR]

Studying deep-water cold seep systems is of great significance to gas hydrate exploration due to their close relationship. Various cold seep systems and related gas hydrate accumulations have been discovered in the northern South China Sea in the past three decades. Based on high-resolution seismic data, subbottom profiles, in situ submergence observations, deep drilling and coring, and hydrate gas geochemical analyses, the geological and geophysical characteristics of these cold seep systems and their associated gas hydrate accumulations in the Qiongdongnan Basin, the Shenhu area, the Dongsha area, and the Taixinan Basin have been investigated. Cold seep systems are present in diverse stages of evolution and exhibit various seabed microgeomorphic, geological, and geochemical features. Active cold seep systems with a large amount of gas leakage, gas plumes, and microbial communities and inactive cold seep systems with authigenic carbonate pavements are related to the variable intensity of the gas-bearing fluid, which is usually derived from the deep strata through mud diapirs, mud volcanoes, gas chimneys, and faults. Gas hydrates are usually precipitated in cold seep vents and deeper vertical fluid migration pathways, indicating that deep gas-bearing fluid activities control the formation and accumulation of gas hydrates. The hydrocarbons collected from cold seep systems and their associated gas hydrate reservoirs are generally mixtures of biogenic gas and thermogenic gas, the origin of which is generally consistent with that of deep conventional gas. We also discuss the paragenetic relationship between the gas-bearing fluid and the seafloor morphology of cold seeps and the deep-shallow coupling of gas hydrates, cold seeps, and deep petroleum reservoirs. It is reasonable to conclude that the deep petroleum systems and gas-bearing fluid activity jointly control the development of cold seep systems and the accumulation of gas hydrates in the northern South China Sea. Therefore, the favorable areas for conventional oil and gas enrichment are also prospective areas for exploring active cold seeps and gas hydrates. [ABSTRACT FROM AUTHOR]

The density of the ocean varies unevenly along the vertical axis. In the presence of external disturbances, internal solitary waves (ISWs) are generated. The strong shear flow field induced by ISW seriously threatens the operational safety of marine structures. Therefore, it has become a hot spot to study the force law of marine structures in ISW. The existing studies are conducted when the ISW parameters are known. However, ISW is not visible in real situations, which leads to difficulties in obtaining ISW parameters. Therefore, it is of great engineering value to accomplish real-time force prediction of marine structures without knowing the ISW parameters in advance. To fill the gap, this study proposes a novel hydrodynamic prediction model with a sensor array as the sensing system and a deep learning algorithm as the decision-making system. The model successfully achieves accurate prediction of the shear stress on the cylinder in the ISW. In addition, a technique for optimizing sensor placement is proposed. This will help identify critical regions in the graphical representations to enhance exploration of flow field information. The results demonstrate that the prediction accuracy of the optimized sensor layout scheme surpasses that of randomly deployed sensors. As a result, this study will provide an important assurance for the safe operation of marine structures. [ABSTRACT FROM AUTHOR]

Understanding the spatial and temporal distribution of different paleontological communities in the southern South China Sea (SCS) is fundamental to explore its paleoclimatic and paleoenvironmental changes. In this study, foraminifera, pollen and diatoms from 100 surface sediment samples covering 40 000 km2 of sea floor in the southern SCS were comprehensively investigated in terms of their assemblage and distribution. The results showed the existence of abundant foraminifera and pollen in most of the samples, although diatom communities were relatively scarce. Foraminifera were dominated by G. sacculifer, G. menardii, G. ruber, while diatoms were characterized by T. simonsenii, T. nitzschioides and T. longissima, indicating a typical tropical marine environment. The pollen assemblages showed a better reflection of montane rainforest, tropical rainforest and mangrove. The spatial differences among foraminifera assemblages may indicate the effect of water depth and a warmer environment in the southeast part of the study area, while the spatial patterns of diatom and pollen assemblages imply the influence of coastal current. Our study also noted that the compositions of paleontological communities in the SCS can vary significantly in a short distance, and synthesized studies on multiple biological groups are needed to reconstruct the Quaternary climate and the oceanographic environment. [ABSTRACT FROM AUTHOR]

With the exploration, development, and research of deep‐sea resources, there is an urgent need for long‐term and continuous observation data of the deep‐sea seabed boundary layer. The traditional method of deep‐sea seabed survey and sampling based on scientific research vessels has the discontinuity of observation data in space and time scales. There are some problems in the seabed in situ observation method based on the seabed observation network for low mobility and high operation and maintenance costs, restricting the in‐depth understanding of the dynamic change process of the deep‐sea floor. To solve the above problems, an open and modular data acquisition control system was designed based on an embedded system and signal processing technology. In terms of the physical, chemical, geological, and ecosystem characteristics of the seafloor or near the seafloor boundary layer, various functional sensors and instrumentation were matched to form an independent underwater integrated measurement or experimental device, eventually realizing in situ multiparameter and long‐time series observations of the seafloor. The system data acquisition and control test were completed through laboratory experiments, which verified the feasibility of the system design. The research showed important theoretical and technical reference significance for the exploration and development of resources in the submarine boundary layer and the promotion of deep‐sea scientific research. [ABSTRACT FROM AUTHOR]

Observations of currents and temperatures from four moorings deployed around the deep slope (∼2500 m) of Caiwei Guyot in the Pacific Prime Crust Zone were utilized to investigate topographically trapped waves at low-latitude seamounts. Contrasting with commonly reported persistent diurnal seamount-trapped wave cases at middle and high latitudes, the subinertial variability in deep currents and temperatures at the slope of Caiwei Guyot was primarily characterized by two distinct lower-frequency bands (i.e., 13–24 and 3.3–4.7 days). These subinertial variabilities are interpreted as intermittent seamount-trapped waves and topographic Rossby waves (TRWs). During certain time periods, the observations include key signatures of seamount-trapped waves, such as near-opposite phases of azimuthal velocity (and temperature) on opposite flanks of the seamount, and patterns of temporal current rotation consistent with counterrotating cells of horizontal current propagating counterclockwise around the seamount. After comparing these observations to idealized seamount-trapped wave solutions, we conclude that the 13–24-day (3.3–4.7-day) energy is mainly due to radial–vertical mode 5 (3) for azimuthal wavenumber 1 (3). Sometimes the subinertial energy remained pronounced at only one flank of the seamount, primarily explained as TRWs with 192–379-m vertical trapping scale and 14–28-km wavelength. Upper-layer mesoscale perturbations might provide energy for deep seamount-trapped waves and TRWs. This study highlights the role of topographically trapped waves in modulating the deep circulation at low-latitude seamounts. [ABSTRACT FROM AUTHOR]

The article presents a study which aims to determine the decomposition temperature of cold seep carbonate through delta carbonate method. The result shows that the carbon dioxide content yielded from all the eight samples increase gradually with time and pyrolysis temperature. Carbon isotopic composition of carbon dioxide reveals distinct isotopic-change tend of two groups with time increase and temperatures.

Integrated investigations have revealed abundant resources of gas hydrates on the northern slope of the South China Sea (SCS). Regarding the gas hydrate research of northern SCS, the gas hydrate related environment problem such as seabed landslides were also concentrated on in those areas. Based on 2D seismic data and sub-bottom profiles of the gas hydrate areas, submarine landslides in the areas of Qiongdongnan, Xisha, Shenhu, and Dongsha have been identified, characterized, and interpreted, and the geophysical characteristics of the northern SCS region investigated comprehensively. The results show 6 major landslides in the gas hydrate zone of the northern SCS and 24 landslides in the Shenhu and Dongsha slope areas of the northern SCS. The landslide zones are located mainly at water depths of 200–3000 m, and they occur on the sides of valleys on the slope, on the flanks of volcanoes, and on the uplifted steep slopes above magmatic intrusions. All landslides extend laterally towards the NE or NEE and show a close relationship to the ancient coastline and the steep terrain of the seabed. We speculate that the distribution and development of submarine landslides in this area has a close relationship with the tectonic setting and sedimentary filling characteristics of the slopes where they are located. Seismic activity is the important factor controlling the submarine landslide in Dongsha area, but the important factor controlling the submarine landslides in Shenhu area is the decomposition of natural gas hydrates. [ABSTRACT FROM AUTHOR]

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. Plain Language Summary: Carbonate mineral precipitation through removing seawater dissolved inorganic carbon—the marine carbonate factory—plays a critical role in shaping marine carbon cycling and global climate. The formation of authigenic carbonate from pore‐water of marine sediments represents a variable share of the marine carbonate factory throughout geological history. However, it is challenging to quantify the extent of such authigenic carbonate formation. By analyzing pore‐water parameters from 153 sites influenced by methane diffusion of the northern South China Sea, we found a significant positive correlation between the rate of carbonate precipitation and the diffusive flux of sulfate into shallow sediments. Given the existence of estimates on the sizes of the seawater sulfate pool and diffusive fluxes of sulfate into sediments over Earth's history, we propose that the observed correlation can be used for quantifying authigenic carbonate formation in shallow sediments along continental margins through time, which will greatly advance our understanding for past carbon cycling and its relation to climate. Key Points: Porewater parameters from 153 sites of the northern South China Sea were evaluated to quantify the extent of authigenic carbonate formationRate of carbonate formation strongly correlates with diffusive flux of sulfate into sediments affected by methane diffusionA correlation of carbonate formation rate with sulfate flux is used to quantify most of authigenic carbonate formation in shallow sediments [ABSTRACT FROM AUTHOR]

Deep‐sea environments are the largest ecosystem of the global biosphere and constitute a crucial role in global biogeochemical cycles. We integrated biogeochemical and molecular ecological approaches to investigate microbial activity and diversity, with the goal of elucidating pathways and regulations of methane cycling and low molecular weight (LMW) compounds metabolism in different deep‐sea sediments of the South China Sea. We found that methanogenesis, anaerobic oxidation of methane, and sulfate reduction occurred concurrently with low rates in surface sediments of the Haima area (~ 50 cm push cores) and in subsurface sediments of the Shenhu area (~ 8 m piston core). In the presence of sulfate, methanogenesis was fueled by methylotrophic substrates, in agreement with thermodynamic calculations as well as the detection of the methylotrophic methanogenic genus Methanococcoides. Higher oxidation rates of LMW compounds than methanogenesis rates, suggested acetate, and to a lesser extent, methanol and methylamine, were predominantly utilized as an energy source by nonmethanogenic microorganisms (e.g., sulfate‐reducing bacteria). Diverse methanotrophic archaea (e.g., ANME‐1a/b and ANME‐2a/b) and sulfate‐reducing bacteria (e.g., Desulfarculaceae and Desulfobacteraceae) were observed and the abundance of mcrA and dsrA genes varied over depth and between sites. Dominant archaeal groups, such as Bathyarchaeota, Thermoplasmatale, Woesearchaeota, Lokiarchaeota, were consistently detected at both areas. Multivariate statistical analysis demonstrated sulfate was the most relevant environmental variable that correlated with the archaeal community composition. These results suggested that the presence of sulfate controlled methane cycling and LMW carbon metabolism pathways, and also affected the composition of the microbial community. [ABSTRACT FROM AUTHOR]

Fluid flow patterns at cold seeps provide insights into the mechanism and influence of methane emission into the ocean, which is critical in its environmental impact assessment. Here, we report pore fluid compositions of three ∼8 m long piston cores (QDN-14A, QDN-14B and R1) collected from the newly-discovered active Haima cold seeps on the northwestern slope of the South China Sea. Reaction-transport models were further applied to quantify related biogeochemical processes and to reveal the patterns of fluid flow. Extremely low δ13C values (<−52‰) of dissolved inorganic carbon (DIC) near the sulfate-methane transition in the three cores suggest that anaerobic oxidation of methane is the predominant biogeochemical process. The presence of small pieces of gas hydrates along with negative anomalies of porewater chloride and sodium concentrations reflects gas hydrate dissociation. Nearly invariable concentrations of sulfate, DIC, and calcium on a meter-scale were observed in the uppermost part of the sediment cores QDN-14A and QDN-14B. This irrigation-like feature is inferred to result from enhanced methane flux in QDN-14A and QDN-14B. We infer that lateral migration of methane-rich fluids from R1 site to QDN-14A and QDN-14B sites together with upward migrated methane is responsible for the enhanced methane flux. This speculation is supported by the occurrence of gas hydrates which might have clogged the fluid channel in the seepage center (R1) and driven the transportation of methane-bearing fluid along a coarser sediment layer in surrounding sediments (QDN-14A and QDN-14B). The proposed scenario is further demonstrated using a non-steady-state modeling that reconstructed the porewater irrigation-like feature assuming an increased methane flux. The modeling result predicts that gas-hydrate formation in core R1 started at least 150 yr B.P. The proposed fluid flow pattern within a localized seep site may have a great implication for understanding the heterogeneity of sedimentary records. • Pore fluid compositions at newly-discovered active cold seeps were reported in the SCS. • Numerical simulations were used to reveal fluid flow patterns at Haima cold seeps. • The lateral migration of fluid might prevail at the seeping area of Haima cold seeps. • The lateral migration of fluid is caused by the sealing of gas hydrates in the seeping center. [ABSTRACT FROM AUTHOR]

The sources and sinks of dissolved CH4 in offshore waters are becoming diversified with the rapid increase in human activities. The concentration and air–sea exchange flux of dissolved CH4 present new characteristics of more intense spatiotemporal evolution, and the contribution to atmospheric CH4 continues to increase. Herein, a new model based on navigable air–sea exchange flux observations was proposed, which replaced the traditional station-based sampling analysis and testing method, realizing the synchronous measurement of methane in the atmosphere and surface seawater carried by ships. Based on the Marine Geological Survey project of the China Geological Survey, comprehensive environmental surveys were conducted in April 2018, September 2018, and June 2019 in the Qiongdongnan area in the northern part of the South China Sea, and the dissolved methane content in the sea surface atmosphere and surface seawaters in 2019 were simultaneously obtained. The methane exchange flux ranges of the southeastern sea area were calculated as −0.001~−0.0023 μmol·m−2·d−1 and −0.00164~−0.00395 μmol·m−2·d−1 by using the Liss and Merlivat formula (LM86), the Wanninkhof formula (W92), and the field-measured wind speed. The feasibility of the navigational air–sea methane exchange flux observation system was proven in a sea trial, and the measurement accuracy and observation efficiency of air-sea flux were improved with the designed system, providing a new technical means for further research on multiscale air–sea interactions and global climate change. [ABSTRACT FROM AUTHOR]

Cold hydrocarbon seepage is a frequently observed phenomenon along continental margins worldwide. However, little is known about the impact of seeping fluids on the geochemical cycle of redox-sensitive elements. Pore waters from four gravity cores (D-8, D-5, D-7, and D-F) collected from cold-seep sites of the northern South China Sea were analyzed for SO 4 2− , Mg 2+ , Ca 2+ , Sr 2+ , dissolved inorganic carbon (DIC), δ 13 C DIC , dissolved Fe, Mn, and trace elements (e.g. Mo, U). The sulfate concentration–depth profiles, δ 13 C DIC values and (ΔDIC+ΔCa 2+ +ΔMg 2+ )/ΔSO 4 2− ratios suggest that organoclastic sulfate reduction (OSR) is the dominant process in D-8 core. Besides OSR, anaerobic oxidation of methane (AOM) is partially responsible for depletion of sulfate at D-5 and D-7 cores. The sulfate consumption at D-F core is predominantly caused by AOM. The depth of sulfate–methane interface (SMI) and methane diffusive flux of D-F core are calculated to be ~7 m and 0.035 mol m −2 yr −1 , respectively. The relatively shallow SMI and high methane flux at D-F core suggest the activity of gas seepage in this region. The concentrations of dissolved uranium (U) were inferred to decrease significantly within the iron reduction zone. It seems that AOM has limited influence on the U geochemical cycling. In contrast, a good correlation between the consumption of sulfate and the removal of molybdenum (Mo) suggests that AOM has a significantly influence on the geochemical cycle of Mo at cold seeps. Accordingly, cold seep environments may serve as an important potential sink in the marine geochemical cycle of Mo. [ABSTRACT FROM AUTHOR]

During the period from July 2016 to July 2018, a mooring system deployed in the central Andaman Sea recorded a significant number of highly intense mode-2 internal solitary waves (ISWs), with wave-induced current strengths comparable to those of local mode-1 ISWs. Distinct propagation characteristics and seasonal variations are uncovered, with mode-2 ISWs being identified as primarily propagating eastward and exhibiting a notable frequency peak from November to March. A significant correlation is established between the occurrence of mode-2 ISWs and higher-mode internal tides (ITs), particularly characterized by a high correlation with the third Empirical Orthogonal Function (EOF) mode. Combined with satellite remote sensing images, it is further confirmed that mode-2 ISWs are generated by the nonlinear steepening of ITs and propagate over long distances through resonance with higher-mode ITs. In contrast, our findings suggest that mode-1 ISWs are predominantly generated by the Lee-wave mechanism, especially south of the Ten Degree Channel, and typically propagate northeastward. This study underscores the complex interplay of ocean stratification and seabed topography in the genesis and propagation of ISWs. • A two-year long in-situ observation has been conducted on the strong mode-2 internal solitary waves in the central Andaman Sea. • The mode-2 internal solitary waves are primarily generated by the nonlinear steepening of internal tides in the Ten Degree Channel, while most mode-1 internal solitary waves originate south of the Ten Degree Channel, produced by the Lee-wave mechanism. • The internal solitary waves of both modes occur more frequently from November to March and less so from May to August. This is primarily attributed to the local oceanic stratification. • The resonant coupling between the mode-2 internal solitary waves and the higher-mode internal tides is the main reason for the stable propagation of the mode-2 internal solitary waves. [ABSTRACT FROM AUTHOR]

Understanding the controls on the sulfur isotope compositions of syndepositional pyrite (δ34S py) during early diagenesis is critical for environmental reconstructions, especially for the reconstruction of the marine sulfur cycle. Commonly, δ34S py values increase with depth in marine sediments; this phenomenon has been extensively studied, fostering the reconstruction of both global and regional depositional environments. However, more recently a decrease of δ34S py values with depth has been increasingly observed, but the corresponding controls on sulfur stable isotopes remain poorly constrained. This study investigated a gravity core collected from the northern continental slope of the South China Sea. Morphology, content, and δ34S values of pyrite, concentration and sulfur isotopic composition of porewater sulfate (δ34S SO4), carbon, nitrogen, and sulfur contents, and grain sizes of terrigenous sediments were analyzed and AMS14C dating of planktonic foraminifera was conducted. The δ34S py values were found to decrease with depth from −16.8‰ to −42.8‰, indicating low sulfur isotope fractionation (<38‰) during microbial sulfate reduction in the uppermost sediments and a larger fractionation (>64‰) at greater depth. Significant contributions of relatively 34S-enriched pyrite formed at shallow depth leads to overall δ34S py variations >26‰, whereby low δ34S py values coincide with higher sedimentation rates and higher organic matter supply. This study highlights the potential significance for relatively 34S-enriched, shallow-depth pyrite for δ34S py records, which may affect the reconstruction of depositional conditions and the global sulfur cycle. • Relatively 34S-enriched pyrite formed at shallow depth results from low sulfur isotope fractionation during MSR (<38‰). • Higher sedimentation rate and high organic matter supply led to lower δ34S py values. • Relatively 34S-enriched pyrite formed in uppermost sediments causes overall δ34S py variation >26‰. • δ34S py values provide new insight into the global sulfur cycle and past depositional processes. [ABSTRACT FROM AUTHOR]

Internal solitary waves are a special type of non-linear ocean internal waves. Due to their high peak and deep valley, they can cause motion instability and loss of control of submersibles. This work investigates the interaction between large-scale continuously stratified internal solitary waves and an advancing submersible. Based on the fully nonlinear internal solitary wave theory, i.e. Dubriel-Jacobin-Long (DJL) equation, combined with Computational Fluid Dynamics (CFD) simulation, a three-dimensional wave tank is established using an initial flow field wave-making method. The effects of three key parameters, namely submergence depth, wave amplitude, and advancing speed, on the motion response and load characteristics are studied. The results show that the submergence depth has a great influence on the motion response of the submersible, especially for the submersible near the pycnocline. The wave amplitude and advancing speed mainly affect the load on the submersible and the duration of wave-body interaction. Due to the flow characteristics of internal solitary waves, the submersible will experience a bow moment. If the buoyancy suddenly decreases, the submersible will lose its "support" of fluid and sink rapidly. The mechanism of the "falling deep" phenomenon is finally revealed. [ABSTRACT FROM AUTHOR]

Marine methane hydrates are a huge and dynamic carbon reservoir found mainly at the continental margins, and their stability might be affected by climate-associated pressure and temperature changes on the seafloor. Reconstructing the growth history of cold-seep carbonates, which formed during seafloor methane leakage, could help to constrain methane hydrate stability in the geological past. However, U-Th isotope systematics of these complex carbonate cements have not yet been systematically investigated on the micro-scale, leaving uncertainties in the U-series geochronology which is commonly applied to date the seep carbonates. In this study, we have developed multiple in-situ analytical methods, including U-Th isotope analysis by laser ablation MC-ICPMS, elemental concentration mapping by laser ablation ICPMS, as well as organic distribution mapping by Raman Spectroscopy, to provide insights into the U-series geochemistry and geochronology for the different types of cold-seep carbonates. Our result demonstrates that 238U and 232Th of these carbonates are dominantly derived from seawater and detrital particles, respectively. As the [230Th/232Th] (activity ratio) of micro-domains with high [232Th/238U] is negligibly affected by U decay, we have directly determined the initial [230Th/232Th] of the cold-seep carbonates which is 0.7 ± 0.1 (2 SD, n = 12). In general, U-series isotopes show closed-system behavior within our studied analytical precision in the interior of the seep cements, and the initial [230Th/232Th] derived from the isochron approach is consistent with the in-situ direct determination. A notable exception is a calcitic pipe sample with highly enriched U in its rim which has also experienced post-depositional mobilization. Our method is then applied to a large set of seep carbonate samples from the upper continental slope of the northern South China Sea (SCS). The obtained U-series ages provide evidence that cold seep was likely continuously active since at least ∼72 ka in the northern SCS, but the timing and duration of methane leakage vary between different sites within this region. While the upper continental slope methane hydrates are highly susceptible to destabilization under changing bottom water conditions, our extensive dating on seep carbonates from the SCS further indicates that bottom water P-T conditions could exert contrasting impacts on methane hydrate stability at different depths within the same geological setting. Overall, the in-situ U-series geochronological method developed in our study has the potential to date cold-seep carbonates efficiently and reliably, offering new opportunities to probe into the history of methane leakage in the late Quaternary. [ABSTRACT FROM AUTHOR]

Upward diffusion of dissolved methane and associated anaerobic oxidation of methane (AOM) coupled with microbial sulfate reduction (MSR) are widespread in normal hemipelagic sediments of continental margins. The occurrence of authigenic sulfur enrichment in such sediments is usually regarded as an indicator of AOM; however, extensive MSR and authigenic iron sulfide generation also occur in turbidites. Therefore, research attention should be directed toward determining the geochemical features of authigenic sulfur mineralization in methane-rich background sediments and turbidites. Here we report the sedimentology and geochemical composition of sediments from four piston cores (CL30, CL44, CL47, and CL3A) containing turbidite layers from methane-rich areas of the South China Sea. The turbidite layers were deposited at 17–15 kyr BP or earlier during the last glacial period and were located above the present sulfate–methane transition zone (SMTZ). The median grain size, proportion of sand-sized grains, and Si, Ti, K, and Zr contents show marked elevation in the turbidite layers compared with the background sediments, indicating the input of large amounts of terrigenous detrital matter with coarser grains. High total sulfur (TS) contents and low δ34S AIS values (AIS: acid-insoluble sulfur) (−35.2‰ to −26.1‰) are observed within turbidite layers relative to the background hemipelagic sediments in core CL44. These results suggest that intensive sulfidization occurred as a result of enhanced organoclastic sulfate reduction rates in turbidite horizons, which were probably caused by the resultant decrease in downward oxygen flux and waning bioturbation after rapid deposition of turbidites. In comparison, TS contents are higher and δ34S AIS values are positive (0.2‰–46.8‰) within the SMTZ on account of the rapid consumption of sulfate and build-up of isotopically heavier hydrogen sulfide pools via intensive AOM. Moreover, authigenic barium (Ba) enrichments commonly occur in the depth interval immediately above the SMTZ rather than within turbidite layers; therefore, they serve as a useful indicator of the position of the SMTZ. This study presents distinct differences in the geochemical compositions of turbidity deposits and methane-rich background sediments and highlights that a multi-proxy approach including sedimentological and geochemical analyses should be used to constrain the types of MSR in deep-sea sediments, given the common occurrence of turbidites and subsurface methane release in marginal deep-sea areas. It is also suggested that if applied with caution, S–C–Ba geochemical patterns can be used to identify palaeo-SMTZs and palaeo methane-rich zones in turbidite-containing strata. • Both authigenic sulfur enrichment occurred in turbidite and seep sediments in the SCS. • Sulfidization in turbidite layer may be characterized by OSR with high SRR. • Combined S, C, and Ba geochemical patterns can be used to identify turbidite and seeps. [ABSTRACT FROM AUTHOR]

Abstract: In this study, changes in the abundance and distribution of diamondoids in petroleum with thermal maturity were investigated by a simulation oil cracking experiment. Highly sensitive and selective gas chromatography–triple quadrupole mass spectrometry (GC–MS–MS) was employed to quantify diamondoids at ppm and sub-ppm levels. The results indicate that diamondoids were generated primarily within the maturity range 1.0–2.1% EasyRo and destroyed at high thermal maturity (>2.1% EasyRo). Hence, the occurrence of high concentrations of diamondoids probably corresponds to the maturity range from the wet gas to the early dry gas stage (i.e., 1.5–2.5% EasyRo). Good correlations were observed between a few ratios of diamondoids (i.e., EAI, DMAI-1, DMDI-1 and TMAI-1) and EasyRo. This finding indicates that these parameters may be useful maturity indices for organic matter from the late oil window to the dry gas window. [Copyright &y& Elsevier]

Abstract: In this study, headspace single-drop microextraction (HS-SDME) coupled with gas chromatography-flame ionization detection (GC-FID) was tested to determine C6–C12 light hydrocarbons (LHs) in petroleum and aqueous samples. Several significant experimental parameters, such as drop solvent type, drop volume, sample solution ionic strength, agitation speed and extraction time were optimized. Under optimum extraction conditions, specifically, a 1.5μl microdrop of n-hexadecane, 30min extraction of a 5ml aqueous sample placed in a 10ml vial, and stirring at 1000rpm at room temperature, the reproducibility and accuracy of this method were found to be satisfactory. Two examples using this method indicated that HS-SDME is a simple, efficient and promising technique for the determination of volatile C6–C12 LHs in complex matrices. [Copyright &y& Elsevier]

Abstract: In this study, headspace single-drop microextraction (HS-SDME) coupled with gas chromatography-flame ionization detection (GC-FID), was employed to determine short-chain fatty acids (SCFAs) in ruthenium tetroxide (RuO4) oxidation products of asphaltenes. Several significant parameters, such as drop solvent type, drop volume, sample solution ionic strength, agitation speed, extraction time, and ratio of headspace volume to sample volume were optimized. Under optimum extraction conditions (i.e., a 3-μL drop of 1-butanol, 20min exposure to the headspace of a 6mL aqueous sample placed in a 10mL vial, stirring at 1000rpm at room temperature, and 30% (w/v) NaCl content), the reproducibility and accuracy of the method have been tested and found to be satisfactory. The analysis of a real asphaltene sample using this method proved that HS-SDME can be a promising tool for the determination of volatile SCFAs in complex matrices. [Copyright &y& Elsevier]

Summary: Methane is a potent greenhouse gas; methane production and consumption within seafloor sediments has generated intense interest. Anaerobic oxidation of methane (AOM) and methanogenesis (MOG) primarily occur at the depth of the sulfate–methane transition zone or underlying sediment respectively. Methanogenesis can also occur in the sulfate‐reducing sediments through the utilization of non‐competitive methylated compounds; however, the occurrence and importance of this process are not fully understood. Here, we combined a variety of data, including geochemical measurements, rate measurements and molecular analyses to demonstrate the presence of a cryptic methane cycle in sulfate‐reducing sediments from the continental shelf of the northern South China Sea. The abundance of methanogenic substrates as well as the high MOG rates from methylated compounds indicated that methylotrophic methanogenesis was the dominant methanogenic pathway; this conclusion was further supported by the presence of the methylotrophic genus Methanococcoides. High potential rates of AOM were observed in the sediments, indicating that methane produced in situ could be oxidized simultaneously by AOM, presumably by ANME‐2a/b as indicated by 16S rRNA gene analysis. A significant correlation between the relative abundance of methanogens and methanotrophs was observed over sediment depth, indicating that methylotrophic methanogenesis could potentially fuel AOM in this environment. In addition, higher potential rates of AOM than sulfate reduction rates at in situ methane conditions were observed, making alternative electron acceptors important to support AOM in sulfate‐reducing sediment. AOM rates were stimulated by the addition of Fe/Mn oxides, suggesting AOM could be partially coupled to metal oxide reduction. These results suggest that methyl‐compounds driven methane production drives a cryptic methane cycling and fuels AOM coupled to the reduction of sulfate and other electron acceptors. [ABSTRACT FROM AUTHOR]

• Carbonate precipitation rates range from 0.05 to 21 µmol m−2 h−1 at three methane seeps. • Calcium isotopic fractionation of aragonite of −1.8 ± 0.3 ‰ is close to equilibrium fractionation. • Kinetic Ca isotopic fractionation of high-Mg calcite is −0.9 and −0.8 ± 0.3 ‰ at two sites. • Mineralogy is the primary control on Ca isotopic fractionation at methane seeps. The formation of authigenic carbonate in marine environments represents a process that buffers ocean chemistry and atmospheric carbon dioxide levels. The isotopic composition of calcium (δ44/40Ca) in authigenic carbonate can be used to investigate the calcium (Ca) cycle, seawater chemistry, and diagenesis of carbonate rocks, archiving key information on the evolution of the Earth's surface environments. Laboratory experiments have shown that Ca isotopic fractionation during carbonate precipitation – the basis of the δ44/40Ca proxy – is mainly determined by both mineral phase and precipitation rate. However, the precipitation rate of submarine authigenic carbonate is much lower than rates in laboratory experiments. This study investigated the Ca isotopic composition of pore water and carbonate nodules collected from two gravity piston cores and one push core from the Haima seeps in the northern South China Sea. Methane fluxes calculated for the three cores range from 12 to 134 µmol cm−2 yr−1. The core with intermediate methane flux showed evidence of aragonite precipitation, while high-Mg calcite was the dominant mineral phase in the other two cores as indicated by Mg/Ca and Sr/Ca ratios of pore water. Numerical modeling of pore water geochemistry revealed that: (1) precipitation rates of carbonate per unit reactive surface area range from 0.05 to 21 µmol m−2 h−1, which is one to three orders of magnitude lower than rates in precipitation experiments; (2) Ca isotopic fractionation for aragonite precipitation is –1.8 ± 0.3 ‰, close to the reported equilibrium isotopic fractionation in precipitation experiments; and (3) Ca isotopic fractionation for high-Mg calcite precipitation is similar for the two cores (−0.9 ± 0.3 ‰ and −0.8 ± 0.3 ‰), although the modeled precipitation rates differed by two orders of magnitude. These results indicate that mineralogy rather than precipitation rate is the primary control on Ca isotopic fractionation during carbonate precipitation at seeps, resulting in lower δ44/40Ca values of aragonite (0.91±0.06 ‰, N = 4) than of high-Mg calcite (1.41±0.04 ‰, N = 9) reported relative to NIST SRM915a. This study documents distinguishable Ca isotopic fractionation during the formation of methane-derived high-Mg calcite and aragonite, providing fundamental parameters for further exploration of the calcium isotopic composition of marine authigenic carbonates in the geological record. [ABSTRACT FROM AUTHOR]

The gas hydrate deposit in Shenhu, Northern South China Sea (NSCS) was one of the main sources for deep-water hydrocarbon and hydrate. Based on field observations on a gas hydrate deposit among 20 × 20 km2 at Shenhu of the northern continental slope of SCS in May (before drilling) and September (after drilling) in 2015, environmental baseline, comparisons of phytoplankton community, biomass and potential environmental drivers were studied. Results indicated the deposit area was a typical low-nutrients low-chlorophyll a (LNLC) environment, characterized by low phytoplankton abundance and diversity. The maximum of abundance and Chl a were fixed at 75 m before and after drilling, but their decrease was larger from 0.53 mg/m3 to 0.40 mg/m3 and 1218 cells/L to 843 cells/L with non-significance found, respectively. After drilling, ammonium decreased significantly (2.13 μmol/L to 0.20 μmol/L), along with nitrite, salinity and dissolved methane, while pH increased significantly (8.10–8.19). Phytoplankton community was composed of 97 taxa of 47 genera in 4 classes, including diatoms, dinoflagellates, cyanobacteria and chrysophyte. The dominant diatom species before and after drilling remained the same, which included Navicula parva , Pseudonitzchia circumpora and Fragilariopsis doliolus. Dominant dinoflagellates shifted from the cosmopolitan Scrippsiella trochoidea to the warm-water adapted Gyrodinium flavum. The diazotrophic cyanobacterium Trichodesmium thiebaultii become more apparent in higher occurrence and abundance due to alleviation from lower-pH inhibition on nitrogen fixation. Redundancy analysis and Spearman correlation analysis revealed that the dominant species and Chl a were mainly associated to pH, DO and nitrite. The X-bar control chart indicated that a constrained maximum problem of phytoplankton abundance in particular layers (50 m, 75 m and 100 m). We clearly documented in the revisited stations (SH3–W2 and SH3–W14), the decrease of abundance and Chl a and the increase of pH and DO were evident in each sampling layer accompanied with lower dissolved methane associated to in situ anoxic or aerobic microniches activities, but the correlations with dissolved methane were not strong. • The gas hydrate deposit in Shenhu, NSCS was a typical low-nutrients low-chlorophyll environment accompanied with low phytoplankton abundance and diversity • Nitrite, pH and DO were major factors causing phytoplankton fluctuation, while dissolved methane had non-significant impact directly. • Variation of subsurface methane was likely resulted from in situ anoxic or aerobic microniches activities. [ABSTRACT FROM AUTHOR]

The formation of authigenic phosphorus (P) minerals near the sulfate-methane transition (SMT) represents an important pathway of P burial in marine sediments. However, our current understanding of the coupling between the formation of authigenic phosphate and carbon and iron (Fe) cycling is insufficient. In this study, a piston core recovered from the Haima cold seeps of the Qiongdongnan basin, northern South China Sea, was used to analyze pore-water parameters and solid-phase Fe and P speciation. Results from a previous study indicate that the current SMT is located at approximately 1 m below the seafloor (mbsf) and a fossil SMT located at approximately 6.5 mbsf. Dissolved phosphate concentrations and solid-phase iron oxide (Fe Ox) contents are found to decrease with depth, while Fe-bound P (P Fe) and authigenic phosphate (P Auth) contents increase with depth in the zone between the current and fossil SMTs where gas hydrate is present, suggesting that vivianite and authigenic apatite formed in this zone. Gas hydrate below the current SMT will dissociate once methane is undersaturated, which could persistently provide dissolved methane to prevent the downward shift of the current SMT where methane is continually consumed. Such a methane-rich environment maintained by gas hydrate may favor the persistent reduction of Fe Ox and the formation of vivianite. Dissolved phosphate concentrations are high, but decrease rapidly with depth at the fossil SMT. Combined with higher Fe Ox and P Auth contents and lower P Fe contents and lower P Org /total organic carbon (TOC) ratios, these results suggest the formation of authigenic apatite at the fossil SMT. The high dissolved phosphate concentration and low P Org /TOC ratios at the fossil SMT are interpreted to reflect preferential release of P during the degradation of organic matter generated by methanotrophic microorganisms. Overall, our study shows that P speciation in methane-rich sediments provides insight into the formation processes of authigenic P minerals near the SMT and associated carbon and Fe cycling processes. • P and Fe cycling was investigated between the current and fossil sulfate-methane transition (SMT). • An apparent relationship was observed between the occurrence of gas hydrate and the formation of vivianite. • Iron-driven anaerobic oxidation of methane may be the key for a co-occurrence of gas hydrate and vivianite. • Preferential release of P during degradation of organic matter can occur at fossil SMTs. [ABSTRACT FROM AUTHOR]

Highlights • δ34S of pyrite in seep carbonates from Site F and Haima were investigated. • Mo, As, Sb contents and Sr/Ca, Mg/Ca ratios reveal variable redox conditions. • Pyrites in calcite have more positive δ34S values than aragonite at seeps. • The variable δ34S values are useful to assess the intensities of past seepages. Abstract Authigenic carbonates and pyrite associated with sulfate-driven anaerobic oxidation of methane (AOM) at methane seeps provide archives to explore the biogeochemical processes involved and seepage dynamics over time. The wide range and extremely high δ34S values of pyrite (δ34S py) have been used to trace the AOM-related processes. However, the detailed mechanism for this phenomenon is not well understood. We propose that the characteristics of δ34S py were mainly controlled by the competition between sulfate reduction and sulfate supply, as well as the redox condition. To test this hypothesis, we investigated Sr/Ca and Mg/Ca ratios, trace element compositions, pyrite contents and sulfur isotopic compositions in seep carbonates from Site F and Haima in the northern South China Sea. Calcite and aragonite contents were distinguished through the Sr/Ca and Mg/Ca ratios. The data show that aragonites are always associated with relatively low δ34S py values compared to calcites. The Mo contents show a good correlation with pyrite contents in calcites and aragonites, and the slope in aragonites is larger than that in calcites. This relationship indicates that the aragonite precipitated in a relatively open system with higher Mo availability. Thus, we conclude that sulfides with low δ34S values formed at high supply of sulfate under the relatively open system with respect to diffusive replenishment of sulfate, where the carbonate precipitation occurred close to the seafloor due to a strong methane flux. Under vigorous methane flux simultaneously, the high potential of less anoxic conditions, which could limit the additional pyrite accumulation and/or favor the microbial disproportionation, could also be the cause of the low δ34S py , as supported by samples from the Haima sites. Evidence for this assumption is based on the occurrence of bivalve shells and less enrichment in As and Sb. Conversely, the positive δ34S py values result from near to complete exhaustion of dissolve sulfate via AOM within a deeper sulfate-methane transition zone, where Mo is less available. The combination of a detailed elemental study of authigenic carbonates with sulfur isotopic composition of sulfide minerals in carbonates is a promising tool for reconstructing the dynamics of seep intensities at modern and, potentially, geological seep sites. [ABSTRACT FROM AUTHOR]

Graphical abstract Highlights • Sediments from Haima cold seeps have variable compositions. • AOM caused high δ34S CRS and low δ13C TIC values, and high CRS contents. • AOM indicators of sediments are variable under variable methane flux and duration. • Three methane release events were identified in the seep site. Abstract Cold seeps frequently occur at the seafloor along continental margins. The dominant biogeochemical processes at cold seeps are the combined anaerobic oxidation of methane and sulfate reduction, which can significantly impact the global carbon and sulfur cycles. The circulation of methane-rich fluids at margins is highly variable in time and space, and assessing past seepage activity requires the use of specific geochemical markers. In this study, we report multiple sedimentary proxy records for three piston gravity cores (QDN-14A, QDN-14B, and QDN-31) from the Haima seep of the South China Sea (SCS). By combining total organic carbon (TOC), total inorganic carbon (TIC), total nitrogen (TN), total sulfur (TS), acid insoluble carbon and sulfur isotope (δ13C organic carbon and δ34S acid-insoluble), and δ34S values of chromium reducibility sulfur (δ34S CRS), as well as carbon isotopes of TIC (δ13C TIC) in sediments, our aim was to provide constraints on methane seepage dynamics in this area. We identified three sediment layers at about 260–300 cm, 380–420 cm and 480–520 cm sediment depth, characterized by particular anomalies of low δ13C TIC values and high TS content, high TS and CRS contents, and high δ34S acid-insoluble and δ34S CRS values, respectively. On this basis, we propose that these sediment horizons correspond to distinct methane release events preserved in the sediment record. While the exact mechanisms accounting for the presence (or absence) of these particular geochemical signals in the sediment are not known, we propose that they correspond to variations in methane flux and their duration through time. Overall, our results suggest that sedimentary carbon and sulfur and their isotopes are useful tracers for better understanding of methane seepage dynamics over time. [ABSTRACT FROM AUTHOR]

Highlights • Lipid biomarker patterns of active Haima seep carbonates were studied. • UCM in seep carbonate reflects the presence of crude oil at Haima seeps. • The predominant consortia in carbonates from both sites were ANME-1/DSS. • Methane seepage was at least intermittently more intense at site ROV2 than at ROV1. Abstract Authigenic carbonates retrieved from sites ROV1 and ROV2 of the Haima hydrocarbon seeps of the South China Sea at approximately 1390 m water depth were studied using lipid biomarker analyses. Abundant molecular fossils of anaerobic methane oxidizing archaea (ANME) and sulfate-reducing bacteria (SRB) with strong 13C-depletions (δ13C values as low as −126‰), in combination with low δ13C carbonate values (−42.7‰ to −36.8‰), provide evidence that anaerobic oxidation of methane (AOM) was the major process driving the precipitation of the studied seep carbonates. The extremely low δ13C values of archaeal biomarkers confirm that biogenic methane was the main carbon source, but the seepage of accessory crude oil is also suggested by the presence of unresolved complex mixtures in the hydrocarbon fractions. A suite of 13C-depleted biomarkers indicate the predominance of ANME-1/ DSS consortia at both sites, which indicates that the studied carbonates formed during low to medium methane flux. Somewhat higher contents of archaeal biomarkers and their stronger 13C-depletion at site ROV2 probably reflect at least temporarily higher seepage intensities than at site ROV1. Abundant bacterial dialkyl glycerol diethers (DAGEs), revealing a large offset of their δ13C values compared to SRB-derived terminally branched fatty acids, were possibly produced by distinct SRB species other than members of the DSS cluster. The encountered hopanoids are attributed to aerobic methanotrophic bacteria based on their moderate 13C-depletion. The application of molecular fossils in combination with their compound-specific isotope signatures is an efficient tool to reconstruct the composition of seepage fluids and seepage intensities. [ABSTRACT FROM AUTHOR]

Highlights • Porewater geochemistry of two piston cores in hydrate drilling areas was investigated. • A numerical model was applied to quantify involved biogeochemical processes. • Methane consumed mainly originated from external sources rather than local methanogenesis. • The external methane is most likely to originate from local gas hydrate systems. Abstract Methane of various origins is widespread in the sediments of continental margins, representing a key component of the carbon cycle in the ocean. Its occurrence in shallow marine sediments can be linked to the gas hydrate reservoir in the deep sedimentary column. However, this type of methane is difficult to track due to complex reactions occurred during its long distance migration. Porewater geochemical analyses of two ∼7 m piston cores (D17-15 and W01-16) combined with a reaction-transport model were applied to quantify methane-related biogeochemical processes and to explore the linkage of shallow methane to gas hydrate reservoir in the hydrate drilling areas of Shenhu and Dongsha in the South China Sea (SCS). The model results revealed that anaerobic oxidation of methane (AOM) is the predominant biogeochemical process in both cores, consuming approximately 85% and 74% of sulfate in the modeled domain, respectively. The crossplot of dissolve inorganic carbon (DIC) accumulation versus sulfate depletion of the system suggests that methane consumed during the AOM is mainly originated from external methane sources rather than local methanogenesis. Using a δ13C DIC mass balance calculation together with model-derived fractions of different DIC sources, we estimated that the δ13C value of the external methane in core D17-15 is −66.6‰, which is in accordance with the previous reported δ13C values of hydrate-bound methane in the area. These results suggest that methane consumed in shallow sediments in the hydrate drilling areas of the SCS is mainly originated from local gas hydrate reservoir. The proposed approach has the potential to be used to differentiate the sources of methane, which will provide constraints on dynamics of methane in gas hydrate-bearing marine sediments. [ABSTRACT FROM AUTHOR]

Methane seepage activity caused by gas hydrate dissociation plays an essential role in the global carbon cycle and climate change in Earth's history. However, the triggering mechanisms of gas hydrate dissociation remain elusive because of the lack of a relatively complete history of methane seeps on long-term timescales. Here, we present major and trace elements, stable C–O isotopes, and U–Th dating analyses for cold seep carbonates from drill cores in the South China Sea. Our results reveal a 209,00-year-old history of methane seepage activity, which involves multi-stage changes in seepage intensity and methane source (microbial or thermogenic). Chronological data suggest that hydrostatic pressure reduction and dynamic depositional environment mainly controlled the gas hydrate dynamics in the northwestern South China Sea, which is different from the gas hydrate dissociation in the northeastern South China Sea controlled by bottom water warming. This discrepancy may be caused by the differences in physicochemical conditions (e.g., water depth) in different sea areas. Therefore, the findings of this study help to further clarify the relationship between oceanic hydrate reservoirs and environmental change in other world regions. • Seep carbonates from drill cores in the Qiongdongnan Basin were investigated. • Two methane seepage events were identified in the northwestern South China Sea. • Multi-stage changes in seepage intensity and methane source. • Seepage activity controlled by hydrostatic pressure and depositional environment. [ABSTRACT FROM AUTHOR]

Chemosymbiotic bivalves harboring endosymbiotic, chemotrophic bacteria have been investigated from a variety of hydrocarbon seeps worldwide. It has been shown that carbon, nitrogen, and sulfur isotopic compositions of the animal soft body parts are excellent indicators for evaluating energy transfer and food sources for the respective deep-sea habitats. However, recognition of chemosymbiosis has proven to be difficult for bivalves that dwelled at ancient seeps due to the lack of soft tissue. Here, we investigated δ 13 C, δ 15 N, and δ 34 S signatures of the tissue (mantle) and the shell organic matrix (SOM) of the same specimens of three bathymodiolin mussel species with different chemotrophic symbionts (methanotrophs in Bathymodiolus platifrons and B. childressi and thiotrophs in B. aduloides ) and one vesicomyid clam ( Calyptogena sp.) from a variety of hydrocarbon seeps from the South China Sea and the Gulf of Mexico. The data obtained demonstrate that all seep bivalves regardless of species or locations reveal overall small differences in δ 13 C (≤+4‰), δ 15 N (≤+1‰), and δ 34 S (≤+5‰) values between SOM and mantle (∆ SOM-mantle ) of the specimens. Relatively larger ∆ SOM-mantle for δ 13 C values (as high as +10‰) in B. platifrons and larger ∆ SOM-mantle for δ 34 S values (up to 16‰) in B. aduloides and Calyptogena sp. might be due to different symbionts in their gills. Since SOM can be extracted from fossil bivalve shells, the proxy can be used as a fingerprint of chemosynthesis-based food chains, although its utility will depend on the quality of preservation of the shell organic matter. Despite this uncertainty, the new proxy has great potential to reconstruct energy flow through different types of chemosynthesis-based ecosystems. [ABSTRACT FROM AUTHOR]

Sediments at marine methane seep sites provide potential archives of past fluid flow that serve to explore seepage activities over time. Three gravity cores (D-8, D-F, and D-7) were collected from seep sites on the northern slope of the South China Sea where gas hydrates were drilled in the subsurface. Various carbon and sulfur contents, δ 13 C values of total inorganic carbon (δ 13 C TIC ), δ 34 S values of chromium reducible sulfur (δ 34 S CRS ), trace element contents, grain size, and AMS 14 C dating of planktonic Foraminifera in the sediments were determined to explore the availability of related proxies at seeps and to trace past methane seepage activities. Evidence for the presence of methane seepage and consequently anaerobic oxidation of methane comes from the occurrence of 13 C-depleted authigenic carbonate nodules (δ 13 C values as low as −49‰) discovered at an interval of 150–200 cm in core D-7. This finding is supported by high S/C ratios and molybdenum enrichment in the same interval. However, low contents of CRS and negative δ 34 S CRS values are present. It is suggested to reflect a transient methane seepage event, which continued for about 1 ka based on the 14 C ages. Cores D-8 and D-F have δ 13 C TIC values close to zero, low S/C ratios and CRS contents, negative δ 34 S CRS values, and no trace element enrichment, suggesting a negligible impact of methane-seepage on the sediments. The negative δ 34 S CRS values of the studied seep-impacted and background sediments suggest that the application of δ 34 S CRS alone as a proxy to identify AOM-related process may be insufficient. Sediment carbon-sulfur-trace element systematics and 14 C ages used here have the potential to be a promising tool to recognize transient methane seepages and constrain their timescales. [ABSTRACT FROM AUTHOR]

On the basis of the results of simulation experiments, now we better understand the contribution of high carbon number hydrocarbons to diamondoid generation during thermal pyrolysis of crude oil and its sub-fractions (saturated, aromatic, resin, and asphalene fractions). However, little is known about the effect of volatile components in oil on diamondoid generation and diamondoid indices due to the lack of attention to these components in experiments. In this study, the effect of volatile components in oil on diamondoid generation and maturity indices was investigated by the pyrolysis simulation experiments on a normal crude oil from the HD23 well of the Tarim Basin and its residual oil after artificial volatilization, combined with quantitative analysis of diamondoids. The results indicate that the volatile components (≤ nC) in oil have an obvious contribution to the generation of adamantanes, which occurs mainly in the early stage of oil cracking (Easy R<1.0%), and influences the variations in maturity indices of adamantanes; but they have no obvious effect on the generation and maturity indices of diamantanes. Therefore, some secondary alterations e.g., migration, gas washing, and biodegradation, which may result in the loss of light hydrocarbons in oil under actual geological conditions, could affect the identification of adamantanes generated during the late-stage cracking of crude oil, and further influence the practical application of adamantane indices. [ABSTRACT FROM AUTHOR]

Branched glycerol dialkyl glycerol tetraethers (brGDGTs), likely produced by bacteria in soil and peat, are widely distributed, easily detected, newly adopted biomarker compounds. In this study, brGDGTs were used to explore the relationship between the absolute abundance of brGDGTs and the distribution of oil and gas fields in the Duoshiqiao area of the Jiyang depression. The results showed that the concentrations at the Xiakou fault and in the oil and gas fields were obviously higher than those in the contrast areas. The clear relationship among the concentration of brGDGTs, the distribution of oil and gas fields, and the acidolysis hydrocarbon (ethane) indicates that the concentration effectively responds to hydrocarbon seeps from the oil and gas field below. brGDGTs may become some of the most important indicators in surface geochemical prospecting for oil and gas. [ABSTRACT FROM AUTHOR]

Sulfate-driven anaerobic oxidation of methane (SD-AOM) and organoclastic sulfate reduction (OSR) are the two processes that consume sulfate in methane-rich marine sediments. Determining the relative contribution of each process to overall sulfate reduction is critical to assess the global carbon and sulfur cycle in marine settings. The analysis of sulfur and oxygen isotope compositions of porewater sulfate (δ18O SO4 and δ34S SO4) provides crucial insight into sulfate reduction pathways and the dynamics of the sedimentary sulfur cycle. The δ18O SO4 /δ34S SO4 ratio is governed by net sulfate reduction rates and has been widely used to distinguish SD-AOM from OSR. Furthermore, δ18O SO4 /δ34S SO4 slopes are believed to vary with changing methane flux. To enhance the applicability of δ18O SO4 vs. δ34S SO4 plots for the tracing of SD-AOM activity and methane flux, we investigate sulfate sulfur and oxygen isotopes of porewaters from three piston cores collected from the Haima seeps of the South China Sea. Reaction-transport modeling previously indicated that sulfate consumption was dominated by SD-AOM under changing methane fluxes (1126 mmol m−2 yr−1 to 26 mmol m−2 yr−1). Our new data demonstrate an increase of the initial δ18O SO4 /δ34S SO4 slope when methane flux decreases. An initial slope of 0.43 corresponds to a methane flux of 194 mmol m−2 yr−1, the lowest currently known methane flux producing a small δ18O SO4 /δ34S SO4 slope diagnostic for SD-AOM in sediments close to the seafloor. When methane flux decreases to 26 mmol m−2 yr−1, a small slope (0.48) is only observed in deeper sediment layers. Our results also reveal an increase of δ18O SO4 /δ34S SO4 slopes with decreasing SD-AOM rates. We estimate that net sulfate reduction rates can be as low as 10−9 mol cm−3 yr−1 to produce slopes smaller than 0.5 in SD-AOM-dominated settings. In OSR-dominated settings, δ18O SO4 /δ34S SO4 slopes tend to be significantly higher than 0.5, while net sulfate reduction rates tend to be lower than 10−5 mol cm−3 yr−1. This study reveals that quantification of methane flux is required to utilize the full potential of δ18O SO4 vs. δ34S SO4 plots in the endeavor of tracing SD-AOM activity and the dynamics of the sulfur cycle in methane-rich environments. [ABSTRACT FROM AUTHOR]

Abstract: In this study, headspace single-drop microextraction (HS-SDME) coupled with gas chromatography–isotope ratio mass spectrometry (GC–IRMS), was employed to determine compound specific carbon isotopic values (δ13C) of gasoline range hydrocarbons. The reproducibility of the method was found to be satisfactory. By comparison with the δ13C values of the twelve target compounds determined using direct injection of their n-C16 solution, no obvious isotopic fractionation was observed during the HS-SDME procedures. Some parameters that could affect the carbon isotopic fractionation, such as ionic strength of working solutions and inlet split ratio, were examined. The results also suggest that these factors had no significant effect on the carbon isotopic determination of gasoline range hydrocarbons. The application of HS-SDME to a crude oil sample proved that this method could be a promising tool for the determination of carbon isotopic values of gasoline range hydrocarbons in oils or aqueous samples. [Copyright &y& Elsevier]

Abstract: In this study, hollow fiber based liquid-phase microextraction (HF-LPME), coupled with GC, GC–MS and GC–IRMS detections, was employed to determine petroleum hydrocarbons in spilled oils. According to the results, the HF-LPME method collected more low-molecular weight components, such as C7–C11 n-alkanes, naphthalene, and phenanthrene, than those collected in conventional liquid–liquid extraction (LLE). The results also showed that this method had no remarkable effect on the distributions of high-molecular weight compounds such as >C18 n-alkanes, C1–C3 phenanthrene, and hopanes. Also, the carbon isotopic compositions of individual n-alkanes in the two preparation processes were identical. Accordingly, HF-LPME, as a simple, fast, and inexpensive sample preparation technique, could become a promising method for the identification of oil spill sources. [Copyright &y& Elsevier]

Marine gas hydrates mostly occur in high-water content and non-diagenetic submarine sediments without tight stratigraphic traps. Therefore, the seepage capability of overlying and underlying strata (OUS) serves as a crucial parameter to analyze hydrate production behaviors. This study focuses on the numerical simulation study on the effects of the seepage capability of OUS on hydrate production behaviors in depressurization-induced production of three-phase hydrate deposits using a horizontal well. As shown by the simulation results, in the early stage of hydrate production, the permeability of the OUS had little effects on gas production rates. In long-term hydrate production, the hydrate deposit with lower permeability OUS has higher cumulative gas production, larger gas-water ratio and hydrate dissociation scope, and less cumulative water production. Moreover, the hydrate production efficiency first decreased rapidly and then tended to be stable as the permeability of OUS increased, and hydrate production behaviors are similar while the permeability of OUS larger than 1.0 mD. Herein, a water-resisting layers were constructed in overlying and/or underlying strata to decrease the seepage capability of OUS. Compared to the original hydrate deposits, the cumulative gas production and gas-water ratio increased by 31% and 147%, respectively but the water production was only 76% on the 5th year of the simulated production in which water-resisting layers were designed. Furthermore, the water-resisting layer in underlying strata produced more significant effects on hydrate production efficiency than the layer in overlying strata. All these indicate that the low-permeability OUS (especially in underlying strata) can restrain fluid invading into hydrate reservoirs, increase the pressure gradient of hydrate reservoirs and significantly improve the hydrate production efficiency during long-term hydrate production. Therefore, water-proof reformation in OUS may be an effective method to improve the energy utilization efficiency and promote the process of hydrate industrialization. However, further research is needed. • Effects of seepage capability of cap strata on hydrate production were studied. • Critical permeability of overlying/underlying strata determined to be 1.0 mD. • Hydrate system with low permeability cap strata has higher energy utilization. • Aquiclude in underlying strata having higher hydrate production efficiency. [ABSTRACT FROM AUTHOR]

The magnesium (Mg) isotopic composition of marine carbonate has been used as a proxy to constrain the geochemical composition of seawater and to trace the global Mg cycle. Sulfate-driven anaerobic oxidation of methane (SD-AOM) is a prominent process that facilitates the formation of marine authigenic carbonate. Yet the understanding of the impact of SD-AOM on the Mg isotope composition of authigenic carbonate under natural conditions is limited. Here we present the analysis of two tubular methane-seep carbonates from the South China Sea. The tubular carbonates reveal a trend of decreasing δ13C values and increasing carbonate contents from the periphery (i.e., the outer surface of the carbonate) to the inner portion (i.e., close to the inner surface of the carbonate pipes). The tubular carbonates are interpreted as former fluid conduits, indicating intense and lasting seepage that apparently increased with time. The observed variability in composition probably results from changes in the intensity of SD-AOM and correlating carbonate precipitation rates. Trends of enrichment of middle rare earth elements (MREEs), molybdenum (Mo), and uranium (U) from the periphery inward indicate more reducing formation conditions toward the inner surface of the former conduit. Along the same transects, δ26Mg values decrease from periphery to inner portion in one tubular carbonate (−2.63‰ to −3.24‰), while δ26Mg values are close to constant for the second tubular carbonate (−3.42‰ to −3.37‰); such patterns highlight the complexity of Mg isotope fractionation during seep carbonate formation. A positive correlation between δ26Mg and δ13C values and a negative correlation between δ26Mg and Mg/Ca molar ratios suggests that enhanced SD-AOM facilitates the incorporation of light Mg isotopes into the carbonate lattice. However, such assumption contradicts with the fact that higher carbonate precipitation rates reduce Mg isotope fractionation due to incomplete dehydration of Mg ions. It is hypothesized that hydrogen sulfide produced by SD-AOM may enlarge the extent of fractionation by weakening the hydration of Mg. If this interpretation is correct, the effect of sulfide on the fractionation of Mg isotopes can even offset or exceed the effect of precipitation rate. Our study indicates that SD-AOM has an effect on the Mg isotope fractionation during carbonate precipitation. Similar effects may have occurred in geological periods with more widespread carbonate authigenesis. A better understanding of the factors affecting the Mg isotopic fractionation during marine carbonate authigenesis is needed to efficiently use this archive of paleoenvironments and element cycling. [ABSTRACT FROM AUTHOR]

Marine sediments represent the largest reservoir of methane on Earth. Anaerobic oxidation of methane (AOM) mediated by anaerobic methanotrophic archaea (ANME) and associated sulfate-reducing bacteria is the main process controlling methane emission from marine sediments. Recent laboratory studies have revealed that ANME or AOM consortia can mediate nitrogen (N) fixation and ammonium assimilation. These processes are known to preferentially utilize 14N rather than the 15N isotope. However, geochemical fingerprints of microbial nitrogen uptake in marine sediments are lacking, limiting our understanding of its role in modern and ancient sedimentary environments. Here we report prominent negative excursions of bulk sediment δ15N values (up to −5‰) at sulfate-methane transitions (SMTs) where ANME show peak abundances in sediments at four sites of the Haima seeps of the South China Sea. Such δ15N excursions are restricted to SMTs, suggesting that 15N depletion results from ANME-mediated nitrogen uptake. We posit that this process is ubiquitous at the SMT – a reaction front in coastal and continental margin sediments worldwide – resulting in similar isotope patterns. Negative δ15N excursions are consequently a promising proxy to track AOM in the geological record and to better constrain carbon and nitrogen cycling in ancient sedimentary environments. [ABSTRACT FROM AUTHOR]

Sulfate-driven anaerobic oxidation of methane (SD-AOM) controls methane release from marine sediments to the ocean. A variety of authigenic precipitates within sediments has been widely used to identify past occurrences of SD-AOM. However, the lack of a systematic evaluation of the formation conditions of these precipitates sometimes impedes the recognition of SD-AOM in past environments characterized by diffusive transport of methane. Carbon, sulfur, and trace element geochemistry of pore-water and sediments was investigated at a site affected by upward methane diffusion in the Shenhu area of the South China Sea. Here, the sulfate-methane transition zone (SMTZ) is located ~7.6 m below the seafloor based on sulfate and methane concentrations. The slope of δ34S vs. δ18O values of sulfate is consistent with diffusive transport of methane. Concentration and isotope profiles of pore-water species point to diffusive rather than advective transport of solutes. Enhanced sulfate reduction inferred from δ34S values of sulfate agrees with the local occurrence of relatively abundant, 34S-enriched iron sulfide minerals. The time required to produce the observed authigenic iron sulfides around the SMTZ is estimated to be ~1.1 ka based on the amount of iron sulfide minerals and the present diffusive flux of sulfate. No enrichment of authigenic carbonate, barium (Ba), and molybdenum (Mo) was detected in the studied sediments. This observation is consistent with the calculation that the current fluxes of pore-water calcium, magnesium, Ba, and Mo are too low to allow for authigenic enrichments. The low fluxes are largely controlled by diffusion, which facilitates the formation of 34S-enriched iron sulfide minerals. The observed enrichment patterns – unlike those of sediments affected by advective seepage – are expected to be prevalent in modern and ancient continental-margin sediments, and may contribute to the identification of past methane-rich zones and overlying SD-AOM zones as sinks for methane in the geological record. [ABSTRACT FROM AUTHOR]