The evidence for the existence of methane seepages in the northern South China Sea:abnormal high methane concentrations in bottom waters

The methane concentration of water samples at five stations collected by the CTD rosette water sampler in the areas of southwest Dongsha Islands and the Xisha Trough was analyzed by the gas-stripping method on aboard ship. It shows abnormal high methane concentrations in near bottom water samples at three stations. In the southwest Dongsha Islands area, the methane concentration of 4.25 and 10.64 nmol/dm3 occurs in near bottom water samples at Stas E105A and E106, respectively. In the Xisha Trough area, the high methane concentrations of 5.17, 8.48 and 8.70 nmol/dm3 in water depths of 1 750, 1 900 and 2 050 m, respectively, have been observed at Sta. E413. It is believed that the abnormal high methane concentrations are generated from the leakage of methane from sediments. Combining with previous geophysical and geochemical data from these two areas, this was probably related to the submarine gas hydrates decomposition and cold seep system. In May 2007, gas hydrate samples were successfully obtained by the drilling in the Shenhu Sea area located in the southwest Dongsha Islands area. It is called for further drilling surveys to confirm the existence of gas hydrate and cold seep system in the Xisha Trough as early as possible.

Identification of functionally active aerobic methanotrophs and their methane oxidation potential in sediments from the Shenhu Area,South China Sea

Large amounts of gas hydrate are distributed in the northern slope of the South China Sea,which is a potential threat of methane leakage.Aerobic methane oxidation by methanotrophs,significant methane biotransformation that occurs in sediment surface and water column,can effectively reduce atmospheric emission of hydrate-decomposed methane.To identify active aerobic methanotrophs and their methane oxidation potential in sediments from the Shenhu Area in the South China Sea,multi-day enrichment incubations were conducted in this study.The results show that the methane oxidation rates in the studied sediments were 2.03‒2.36μmol/gdw/d,which were higher than those obtained by sediment incubations from other areas in marine ecosystems.Thus the authors suspect that the methane oxidation potential of methanotrophs was relatively higher in sediments from the Shenhu Area.After the incubations family Methylococcaea(type I methanotrophs)mainly consisted of genus Methylobacter and Methylococcaea_Other were predominant with an increased proportion of 70.3%,whereas Methylocaldum decreased simultaneously in the incubated sediments.Collectively,this study may help to gain a better understanding of the methane biotransformation in the Shenhu Area.

Preliminary results of environmental monitoring of the natural gas hydrate production test in the South China Sea

Natural gas hydrate (NGH)is considered as one of the new clean energy sources of the 21st century with the highest potential.The environmental issues of NGH production have attracted the close attention of scientists in various countries.From May 10 to July 9,2017,the first offshore NGH production test in the South China Sea (SCS)was conducted by the China Geological Survey.In addition,environmental security has also been effectively guaranteed via a comprehensive environmental monitoring system built during the NGH production test.The monitoring system considered sea-surface atmosphere methane and carbon dioxide concentrations,dissolved methane in the sea water column,and the seafloor physical oceanography and marine chemistry environment.The whole process was monitored via multiple means, in multiple layers,in all domains,and in real time.After the production test,an environmental investigation was promptly conducted to evaluate the environmental impact of the NGH production test. The monitoring results showed that the dissolved methane concentration in seawater and the near-seabed environment characteristics after the test were consistent with the background values,indicating that the NGH production test did not cause environmental problems such as methane leakage.

Multibeam water column data research in the Taixinan Basin:Implications for the potential occurrence of natural gas hydrate

A multi beam sonar survey is carried out in the continental slope of the Taixinan Basin to obtain submarine topographic and water column data. The data are processed to obtain water column images. Anomalous water column images, displaying plume characteristics, are found in gas hydrate enriched areas in the Taixinan Basin.This indicates the presence of natural gas resources in the Taixinan Basin. The multibeam sonar system is shown to provide an accurate and effective approach for detecting sub-sea gas hydrate.

Experimental study on characteristics of pore water conversion during methane hydrates formation in unsaturated sand

Understanding the pore water conversion characteristics during hydrate formation in porous media is important to study the accumulation mechanism of marine gas hydrate.In this study,low-field NMR was used to study the pore water conversion characteristics during methane hydrate formation in unsaturated sand samples.Results show that the signal intensity of T_(2) distribution isn’t affected by sediment type and pore pressure,but is affected by temperature.The increase in the pressure of hydrogen-containing gas can cause the increase in the signal intensity of T_(2) distribution.The heterogeneity of pore structure is aggravated due to the hydrate formation in porous media.The water conversion rate fluctuates during the hydrate formation.The sand size affects the water conversion ratio and rate by affecting the specific surface of sand in unsaturated porous media.For the fine sand sample,the large specific surface causes a large gas-water contact area resulting in a higher water conversion rate,but causes a large water-sand contact area resulting in a low water conversion ratio(C_(w)=96.2%).The clay can reduce the water conversion rate and ratio,especially montmorillonite(C_(w)=95.8%).The crystal layer of montmorillonite affects the pore water conversion characteristics by hindering the conversion of interlayer water.

Forward modeling and inversion of the relation model between the gas content of plume and its seismic attribute

The methane bubble plume attracts interest because it offers direct evidence of seafloor gas leakage and plays an indirect role in the exploration and identification of natural gas hydrate.In this study,based on established plume models and their migration sections,three amplitude-class attributes were extracted from three formations for the migration sections of five plumes,and the correlation between the gas content and seismic attribute was obtained.As the gas content increases,the amplitude attribute correspondingly increases,and the linear correlation is relatively good.Moreover,correlation coefficients between gas content and amplitude attributes are close to 1.0.By using linear fitting,the relation model between the gas content of the plume and the seismic attribute was obtained.The relation model was subsequently used to invert the gas content from a real databearing plume.Comparison of the gas content section of the plume with the attribute section and real seismic section reveals common distribution characteristics,namely,the color of the section in the lower right corner is dark.If the amplitude value is large in the seismic section of the real plume,the amplitude attribute value is also large in the corresponding attribute section,and the inverted value of the gas content is also large(because gas content and amplitude are linearly correlated),which indicates that the plume bubbles of the section in the lower right corner is intensively distributed.Finally,the obtained gas content section of the plume can reflect the distribution of the plume bubble content more simply and intuitively,from which the distribution law of seafloor bubbles can be deduced,and this lays a foundation for the further estimation of the gas content of the plume and hydrate reserves.

P-T stability conditions of methane hydrate in sediment from South China Sea

For reasonable assessment and safe exploitation of marine gas hydrate resource, it is important to determine the stability conditions of gas hydrates in marine sediment. In this paper, the seafloor water sample and sediment sample (saturated with pore water) from Shenhu Area of South China Sea were used to synthesize methane hydrates, and the stability conditions of methane hydrates were investigated by multi-step heating dissociation method. Preliminary experimental results show that the dissociation temperature of methane hydrate both in seafloor water and marine sediment, under any given pressure, is depressed by approximately -1.4 K relative to the pure water system. This phenomenon indicates that hydrate stability in marine sediment is mainly affected by pore water ions.

Sulfate-Methane Transition Depths and Its Implication for Gas Hydrate

The biological removal of CH4 by methanotrophic(CH4-oxidizing)archaea always occurs at a distinct zone which is known as sulfate-methane transition zone(SMTZ).It is an important indication for high methane flux and gas hydrate occurrence.In this study,we collected pore-water data from South China Sea,Carolina Rise and Blake Ridge to analyze the relationship between CH4,SO42−concentration and depth.We found that below the SMTZ,the methane concentration increases continuously with depth and sulfate concentration decrease linearly to zero.In addition,the geochemical data taken from all these sites show that SMTZ is relatively shallow(less than 20 m),which may indicate that these areas have high methane flux.

Velocity-porosity relationships in hydrate-bearing sediments measured from pressure cores,Shenhu Area,South China Sea

Evaluating velocity-porosity relationships of hydrate-bearing marine sediments is essential for characterizing natural gas hydrates below seafloor as either a potential energy resource or geohazards risks.Four sites had cored using pressure and non-pressure methods during the gas hydrates drilling project(GMGS4)expedition at Shenhu Area,north slope of the South China Sea.Sediments were cored above,below,and through the gas-hydrate-bearing zone guided with logging-while-drilling analysis results.Gamma density and P-wave velocity were measured in each pressure core before subsampling.Methane hydrates volumes in total 62 samples were calculated from the moles of excess methane collected during depressurization experiments.The concentration of methane hydrates ranged from 0.3%to 32.3%.The concentrations of pore fluid(25.44%to 68.82%)and sediments(23.63%to 54.28%)were calculated from the gamma density.The regression models of P-wave velocity were derived and compared with a global empirical equation derived from shallow,unconsolidated sediments data.The results were close to the global trend when the fluid concentration is larger than the critical porosity.It is concluded that the dominant factor of P-wave velocity in hydrate-bearing marine sediments is the presence of the hydrate.Methane hydrates can reduce the fluid concentration by discharging the pore fluid and occupying the original pore space of sediments after its formation.

Multi-beam and seismic investigations of the active Haima cold seeps,northwestern South China Sea

To confirm the seabed fluid flow at the Haima cold seeps,an integrated study of multi-beam and seismic data reveals the morphology and fate of four bubble plumes and investigates the detailed subsurface structure of the active seepage area.The shapes of bubble plumes are not constant and influenced by the northeastward bottom currents,but the water depth where these bubble plumes disappear(630–650 m below the sea level)(mbsl)is very close to the upper limit of the gas hydrate stability zone in the water column(620 m below the sea level),as calculated from the CTD data within the study area,supporting the“hydrate skin”hypothesis.Gas chimneys directly below the bottom simulating reflectors,found at most sites,are speculated as essential pathways for both thermogenic gas and biogenic gas migrating from deep formations to the gas hydrate stability zone.The fracture network on the top of the basement uplift may be heavily gas-charged,which accounts for the chimney with several kilometers in diameter(beneath Plumes B and C).The much smaller gas chimney(beneath Plume D)may stem from gas saturated localized strong permeability zone.High-resolution seismic profiles reveal pipe-like structures,characterized by stacked localized amplitude anomalies,just beneath all the plumes,which act as the fluid conduits conveying gas from the gas hydrate-bearing sediments to the seafloor,feeding the gas plumes.The differences between these pipe-like structures indicate the dynamic process of gas seepage,which may be controlled by the build-up and dissipation of pore pressure.The 3D seismic data show high saturated gas hydrates with high RMS amplitude tend to cluster on the periphery of the gas chimney.Understanding the fluid migration and hydrate accumulation pattern of the Haima cold seeps can aid in the further exploration and study on the dynamic gas hydrate system in the South China Sea.

Evaluation of clayed silt properties on the behavior of hydrate production in South China Sea

Gas hydrate is one kind of potential energy resources that is buried under deep seafloor or frozen areas.The first trial offshore production from the silty reservoir was conducted in the South China Sea by the China Geological Survey(CGS).During this test,there were many unique characteristics different from the sand reservoir,which was believed to be related to the clayed silt physical properties.In this paper,simulation experiments,facilities analysis,and theoretical calculation were used to confirm the hydrate structure,reservoir thermo-physical property,and bond water movement rule.And the behavior of how they affected production efficiency was analyzed.The results showed that:It was reasonable to use the structure I rather than structure II methane hydrate phase equilibrium data to make the production plan;the dissociation heat absorbed by hydrate was large enough to cause hydrate self-protection or reformation depend on the reservoir thermal transfer and gas supply;clayed silt got better thermal conductivity compared to coarse grain,but poor thermal convection especially with hydrate;clayed silt sediment was easy to bond water,but the irreducible water can be exchanged to free water under high production pressure,and the most obvious pressure range of water increment was 1.9–4.9 MPa.

南海北部甲烷渗漏活动存在的证据：近底层海水甲烷高浓度异常

用吹扫-捕集法对东沙群岛西南和西沙海槽附近海域5个站位水柱中的甲烷浓度进行了测定,在其中的3个站位发现了甲烷高浓度异常。在东沙群岛西南海域的E105A和E106两站位近底层海水中甲烷浓度均出现异常增加,其值分别为4.25和10.64 nmol/dm3。在西沙海槽附近的E413站位甲烷异常出现在1 750,1 900和2 050 m深的近底层水中,浓度分别达5.17,8.48和8.70 nmol/dm3。在近底层海水中出现的甲烷高浓度异常是由于沉积物下部甲烷渗漏活动造成的,结合前人在这两个海域沉积物的地球物理和化学调查资料,认为可能是与冷泉渗漏或天然气水合物分解有关。2007年5月在探测到甲烷高浓度明显异常的东沙群岛西南神弧海域,获得了天然气水合物的实物样品,但是西沙海槽附近海域近底层水的甲烷高浓度异常是来源于天然气水合物还是来源于冷泉需要进一步加以确认。

Tracing the Methane Events by Stable Carbon Isotopes of Benthic Foraminifera at Glacial Periods in the Andaman Sea

Stable isotopes of carbon and oxygen variations in foraminiferal shells have been widely used in paleo-environment studies.However,studies about the shells of benthic foraminifera in methanehydrate-bearing sediments as reliable geochemical proxies to reconstruct the potential methane release events in the geologic past are rare.In this study,we present the stable carbon and oxygen isotopes of fossil benthic foraminifera including one epifaunal species(Cibicidoides wuellerstorfi)and two infaunal species(Bulimina mexicana and Uvigerina peregrina)from the Site U1447 of IODP 353 Expedition to trace methane events in the Andaman Sea,where one of the thickest and deepest gas hydrate stability zones was discovered.Theδ^(13)C values of benthic foraminifera show that there are eight distinct intervals with negative values in the last~10 Myr,interpreted as a record of long-term fluctuations in methane emission.Six of these methane events occurred during the glacial sea-level lowstands in the last~1.1 Myr.We,therefore,infer that the trigger mechanism for these events might be the hydrate destabilization caused by sea level fall.The methane events that occurred at~2.11 and~5.93 Ma are more likely related to the sudden changes in sedimentation,either slide events or marked variations in sedimentation rate.

Experimental investigation of hydrate formation in water-dominated pipeline and its influential factors

Blockage in water-dominated flow pipelines due to hydrate reformation has been suggested as a potential safety issue during the hydrate production.In this work,flow velocity-dependent hydrate formation features are investigated in a fluid circulation system with a total length of 39 m.A 9-m section pipe is transparent consisted of two complete rectangular loops.By means of pressurization with gas-saturated water,the system can gradually reach the equilibrium conditions.The result shows that the hydrates are delayed to appear as floccules or thin films covering the methane bubbles.When the circulation velocity is below 750 rpm,hydrate is finally deposited as a“hydrate bed”at upmost of inner wall,narrowing the flow channel of the pipeline.Nevertheless,no plugging is observed during all the experimental runs.The five stages of hydrate deposition are proposed based on the experimental results.It is also revealed that a higher driving pressure is needed at a lower flow rate.The driving force of hydrate formation from gas and water obtained by melting hydrate is higher than that from fresh water with no previous hydrate history.The authors hope that this work will be beneficial for the flow assurance of the following oceanic field hydrate recovery trials.

Experimental studies on the P-T stability conditions and influencing factors of gas hydrate in different systems

The P-T stability conditions of gas hydrate in different systems (i.e., solution, silica sand, and marine sediment) were studied using multi-step decomposition method with our experimental equipment. The effects of different ions with various concentrations and sediment grains on the P-T stability conditions of gas hydrate were investigated. The results show that different ions have different influences on the phase equilibrium of gas hydrate. However, the influence of ions is in a similar trend: the larger the concentration, the bigger the P-T curve shifts to the left. For the silica sand, the influence of pore capillarity of coarse particles (> 460 μm) can be negligible. The P-T curve measured in coarse silica is in agreement with that in pure water. However, the influence of pore capillarity of fine particles (< 35 μm) is significant. The maximum reduction value of temperature is 1.5 K for methane hydrate under stable state. The sediment from the South China Sea significantly affects the P-T stability conditions of methane hydrate, with an average reduction value of 1.9 K within the experimental conditions. This is mainly the result of both the pore water salinity and the pore capillarity of sediment. Because the pore water salinity is keeping diluted by the fresh water released from hydrate dissociation, the measured P-T stability points fall on different P-T curves with the decreasing salinity.

东沙群岛海域沉积物游离烃和孔隙水特征及其地球化学意义

对东沙群岛海域HD170和HD196A两个站位,通过系统的顶空气和孔隙水离子取样测试,对柱状样沉积物和底层水中游离甲烷的含量和沉积物孔隙水的离子组成特征以及孔隙水的来源进行了分析。游离气的分析表明,多数沉积物样品中游离甲烷的含量小于20μL/kg,但在HD196A站位,随着沉积物在海底以下埋深的增加,其中的游离甲烷含量迅速增加,在754～774cm,沉积物中游离甲烷的含量达到了7468．66μL/kg,推测其下存在巨大的烃类供应源。孔隙水的^(86)Sr/^(87)Sr同位素测试显示,本文所研究的两个站位沉积物孔隙水来源于正常的海洋沉积过程,而δ^(11)B的特征表明,沉积物中存在着与海水交换的吸附水,并且HD170站位的交换更多。柱状样沉积物孔隙水中,Ca^(2+)、Mg^(2+)与SO^(-2)_4浓度表现出随着深度增加而明显降低的趋势,其中HD196A站位的硫酸盐甲烷界面小于10mbsf,暗示了该站位深部很可能赋存天然气水合物。