Relation between relative permeability and hydrate saturation in Shenhu area, South China Sea

Nuclear magnetic resonance measurements in hydrate-bearing sandstone samples from the Shenhu area, South China Sea were used to study the effect of gas hydrates on the sandstone permeability. The hydrate-bearing samples contain pore-filling hydrates. The data show that the pore-filling hydrates greatly affect the formation permeability while depending on many factors that also bear on permeability; furthermore, with increasing hydrate saturation, the formation permeability decreases. We used the Masuda model and an exponent N = 7.9718 to formulate the empirical equation that describes the relation between relative permeability and hydrate saturation for the Shenhu area samples.

Undrained shear strength evaluation for hydrate-bearing sediment overlying strata in the Shenhu area, northern South China Sea

The undrained shear strength of shallow strata is a critical parameter for safety design in deep-water operations.In situ piezocone penetration tests(CPTU) and laboratory experiments are performed at Site W18-19 in the Shenhu area, northern South China Sea, where China's first marine hydrate exploitation operation is due to be located. The validation of the undrained shear strength prediction model based on CPTU parameters. Different laboratory tests, including pocket penetrometer, torvane, miniature vane and unconsolidated undrained triaxial tests, are employed to solve empirical cone coefficients by statistical and mathematical methods. Finally, an optimized model is proposed to describe the longitudinal distribution of undrained shear strength in calcareous clay strata in the Shenhu area. Research results reveal that average empirical cone coefficients based on total cone resistance, effective resistance, and excess-pore pressure are 13.8, 4.2 and 14.4, respectively. The undrained shear strength prediction model shows a good fit with the laboratory results only within specific intervals based on their compaction degree and gas-bearing conditions. The optimized prediction model in piecewise function format can be used to describe the longitudinal distribution of the undrained shear strength for calcareous clay within all depth intervals from the mud-line to the upper boundary of hydrate-bearing sediments(HBS). The optimized prediction result indicates that the effective cone resistance model is suitable for very soft to firm calcareous clays,the excess-pore pressure model can depict the undrained shear strength for firm to very stiff but gas-free clays,while the total cone resistance model is advantageous for evaluating the undrained shear strength for very stiff and gassy clays. The optimized model in piecewise function format can considerably improve the adaptability of empirical models for calcareous clay in the Shenhu area. These results are significant for safety evaluations of proposed hydrate exploitation projects.

Types,Characteristics and Significances of Migrating Pathways of Gas-bearing Fluids in the Shenhu Area,Northern Continental Slope of the South China Sea

The first marine gas hydrate expedition in China has been conducted by Guangzhou Marine Geological Survey in the Shenhu Area, northern continental slope of the South China Sea. Previous study has analyzed the P-T conditions, geophysical anomalies and saturation calculations of these gas hydrates, but has not documented in detail the migration of gas-bearing fluids in the study area. Based on the interpretations of 2D/3D seismic data, this work identified two types of migration pathways for gas-bearing fluids in the Shenhu area, i.e., vertical and lateral pathways. The vertical pathways（largescale faults, gas chimneys and mud diapirs） presented as steep seismic reflection anomalies, which could be traced downward to the Eocene source rocks and may penetrate into the Late Miocene strata. The deeper gases/fluids might be allowed migrating into the shallower strata through these vertical conduits. However, the distributions showed distinct differences between these pathways. Large-scale faults developed only in the north and northeast of the Shenhu area, while in the drilling area gas chimneys were the sole vertical migration pathways. Since the Pliocene, normal faults, detachment faults and favorable sediments have constituted the lateral pathways in the Shenhu gas hydrate drilling area. Although these lateral pathways were connected with gas chimneys, they exerted different effects on hydrate formation and accumulation. Gas-bearing fluids migrated upward along gas chimneys might further migrate laterally because of the normal faults, thereby enlarging the range of the chimneys. Linking gas chimneys with the seafloor, the detachment faults might act as conduits for escaping gases/fluids. Re-deposited sediments developed at the early stage of the Quaternary were located within the gas hydrate stability zone, so hydrates would be enriched in these favorable sediments. Compared with the migration pathways（large-scale faults and mud diapirs） in the LW3-1 deep-sea oil/gas field, the migration efficiency of the vertical pathways（composed of gas chimneys） in the gas hydrate drilling area might be relatively low. Description and qualitative discrimination of migration pathways in the Shenhu gas hydrate drilling area are helpful to further understand the relationship between good-quality deep source rocks and shallow, mainly biogenicallyproduced, hydrates. As the main source rocks of the Baiyun sag, lacustrine mudstones in the Wenchang and Enping Formations may provide thermogenic methane. Gas chimneys with relatively low migration efficiency created the vertical pathways. Caused by the Dongsha tectonic movement, the release of overpressured fluids might reduce the vertical migration rates of the thermogenic methane. The thick bathyal/abyssal fine-grained sediments since the Late Miocene provided migration media with low permeability. These preconditions may cause carbon isotopic fractionation ofthermogenic methane during long-distance vertical migrations. Therefore, although geochemical analyses indicate that the methane forming gas hydrate in the Shenhu area was mainly produced biogenically, or was mixed methane primarily of microbial origin, thermogenic methane still contribute significantly.

Application of Seismic Interferometric Migration for Shallow Seismic High Precision Data Processing: A Case Study in the Shenhu Area

The stability of submarine geological structures has a crucial influence on the construction of offshore engineering projects and the exploitation of seabed resources. Marine geologists should possess a detailed understanding of common submarine geological hazards. Current marine seismic exploration methods are based on the most effective detection technologies. Therefore, current research focuses on improving the resolution and precision of shallow stratum structure detection methods. In this article, the feasibility of shallow seismic structure imaging is assessed by building a complex model, and differences between the seismic interferometry imaging method and the traditional imaging method are discussed. The imaging effect of the model is better for shallow layers than for deep layers because coherent noise produced by this method can result in an unsatisfactory imaging effect for deep layers. The seismic interference method has certain advantages for geological structural imaging of shallow submarine strata, which indicates continuous horizontal events, a high resolution, a clear fault, and an obvious structure boundary. The effects of the actual data applied to the Shenhu area can fully illustrate the advantages of the method. Thus, this method has the potential to provide new insights for shallow submarine strata imaging in the area.

Distribution of gas hydrate reservoir in the first production test region of the Shenhu area,South China Sea

In May and July of 2017,China Geological Survey (CGS),and Guangzhou Marine Geological Survey (GMGS)carried out a production test of gas hydrate in the Shenhu area of the South China Sea and acquired a breakthrough of two months continuous gas production and nearly 3.1×10^5 m^3 of production. The gas hydrate reservoir in the Shenhu area of China,is mainly composed of fine-grained clay silt with low permeability,and very difficult for exploitation,which is very different from those discovered in the USA,and Canada (both are conglomerate),Japan (generally, coarse sand)and India (fracture-filled gas hydrate).Based on 3D seismic data preserved-amplitude processing and fine imaging,combined with logging-while-drilling (LWD)and core analysis data,this paper discusses the identification and reservoir characterization of gas hydrate orebodies in the Shenhu production test area.We also describe the distribution characteristics of the gas hydrate deposits and provided reliable data support for the optimization of the production well location.Through BSR feature recognition,seismic attribute analysis, model based seismic inversion and gas hydrate reservoir characterization,this paper describes two relatively independent gas hydrate orebodies in the Shenhu area,which are distributed in the north-south strip and tend to be thicker in the middle and thinner at the edge.The effective thickness of one orebody is bigger but the distribution area is relatively small.The model calculation results show that the distribution area of the gas hydrate orebody controlled by W 18/W 19 is about 11.24 km^2,with an average thickness of 19 m and a maximum thickness of 39 m,and the distribution area of the gas hydrate orebody controlled by W11/W17 is about 6.42 km^2,with an average thickness of 26 m and a maximum thickness of 90 m.

Coexistence of natural gas hydrate,free gas and water in the gas hydrate system in the Shenhu Area,South China Sea

Shenhu Area is located in the Baiyun Sag of Pearl River Mouth Basin,which is on the northern continental slope of the South China Sea.Gas hydrates in this area have been intensively investigated,achieving a wide coverage of the three-dimensional seismic survey,a large number of boreholes,and detailed data of the seismic survey,logging,and core analysis.In the beginning of 2020,China has successfully conducted the second offshore production test of gas hydrates in this area.In this paper,studies were made on the structure of the hydrate system for the production test,based on detailed logging data and core analysis of this area.As to the results of nuclear magnetic resonance(NMR)logging and sonic logging of Well GMGS6-SH02 drilled during the GMGS6 Expedition,the hydrate system on which the production well located can be divided into three layers:(1)207.8–253.4 mbsf,45.6 m thick,gas hydrate layer,with gas hydrate saturation of 0–54.5%(31%av.);(2)253.4–278 mbsf,24.6 m thick,mixing layer consisting of gas hydrates,free gas,and water,with gas hydrate saturation of 0–22%(10%av.)and free gas saturation of 0–32%(13%av.);(3)278–297 mbsf,19 m thick,with free gas saturation of less than 7%.Moreover,the pore water freshening identified in the sediment cores,taken from the depth below the theoretically calculated base of methane hydrate stability zone,indicates the occurrence of gas hydrate.All these data reveal that gas hydrates,free gas,and water coexist in the mixing layer from different aspects.

Numerical studies of gas hydrate evolution time in Shenhu area in the northern South China Sea

Although the Shenhu sea area has been a topic and focus of intense research for the exploration and study of marine gas hydrate in China, the mechanism of gas hydrate accumulation in this region remains controversial. The formation rate and evolution time of gas hydrate are the critical basis for studying the gas hydrate formation of the Shenhu sea area. In this paper, based on the positive anomaly characteristics of chloride concentration that measured in the GMGS3-W19 drilling site is higher than the seawater value, we numerically simulated the gas hydrate formation time of GMGS3-W19 site. The simulation results show that the gas hydrate formation rate positively correlates with the chloride concentration when the hydrate reaches the measured saturation. The formation time of gas hydrate in the GMGS3-W19 site is approximately 30 ka. Moreover, the measured chloride concentration is consistent with the in-situ chloride concentration, indicating that the formation rate of gas hydrate at the GMGS3-W19 site is very fast with a relatively short evolution time.

Microbial diversity in the hydrate-containing and-free surface sediments in the Shenhu area, South China Sea

Microbial diversity in the hydrate-containing （sites SH3B and SH7B） and -free （sites SHIB, SH5B, SH5C） sediments collected from the Shenhu area of the South China Sea （SCS） was investigated using 16S rRNA gene phylogenetic analysis. The phylogenetic results indicate difference in microbial communities be- tween hydrate-containing and -free sediments. At the gas hydrate-containing sites, bacterial communities were dominated by Deltaproteobacteria （30.5%）, and archaeal communities were dominated by Miscellaneous Crenarchaeotic Group （33.8%）; In contrast, Planctomycetes was the major group （43.9%） in bacterial communities, while Marine Benthic Group-D （MBG-D） （32.4%） took up the largest proportion in the archaeal communities. Moreover, the microbial communities have characteristics different from those in other hydrate-related sediments around the world, indicating that the presence of hydrates can affect the microbial distribution. In addition, the microbial community composition in the studied sediments has its own uniqueness, which may result from co-effect of geochemical characteristics and presence/absence of hydrate.

Simulation of the Accumulation Process of Biogenic Gas Hydrates in the Shenhu Area of Northern South China Sea

Previous work has largely discussed the relations between sediment structures and accumulation of gas hydrates in the Shenhu area of South China Sea, but has not documented why the gas hydrates occurred at the seafloor topographic highs. Many gas hydrate exploration examples abroad also indicate that the saturation of gas hydrates was higher at seafloor topographic highs. This work aims to understand why gas hydrates accumulated at topographic highs and why their saturation is higher.

Potential Effects of Some Environmental Factors on a Dinoflagellate Red Tide Caused by Gymnodinium catenatum in Shenhu Bay in 2017

In this study, some environmental factors were investigated to assess the potential effects on the dynamics of a dinoflagellate red tide caused by Gymnodinium catenatum in Shenhu Bay coastal waters in June, 2017. The highest cell density of G. catenatum was 1.0×10 6 cells/L, so it was known as the predominant species of the red tide discovered in Fujian coastal waters for the first time. Continuous rainfall process brought many land-based pollutants into the coastal waters, providing abundant nutrients for plankton growth. Then the continuous sunny and hot weather, high temperature, high salinity and south wind conditions accelerated the formation and occurrence of the red tide. During the red tide, DO, pH and COD increased remarkably and had significant positive correlations with the cell density of the red tide organisms. The contents of various nutrients decreased obviously, and eutrophication index E became low before and after the red tide, indicating the oligotrophic status of Shenhu Bay coastal waters. It is also found that DIP was one of the determinant environmental factors that induced the red tide. The N/P ratio of water in the declining phase of the red tide was close to the Redfield ratio. As for DIN, NH + 4-N and NO - 3-N were the two main species of inorganic nitrogen needed for this red tide dinoflagellate. The study indicates the relationship between the occurrence of the red tide and environmental conditions, providing essential reference for monitoring and forecasting research of red tide in marine environment and ecosystem management.

Revision of P-wave Velocity and Thickness of Hydrate Layer in Shenhu Area, South China Sea

To revise P-wave velocity and thickness of the hydrate layer in the Shenhu area of the South China Sea, acoustic and resistivity logging curves are reanalyzed. The waterlogging phenomenon is found in the shallow sediments of five drilling wells, which causes P-wave velocity to approximate the propagation velocity of sea water(about 1500 m s-1). This also affects the identification of the hydrate layer and results in the underestimate of its thickness. In addition, because there could be about a 5 m thick velocity ramp above or below the hydrate layer as interpreted by acoustic and resistivity logging curves, the recalibrated thickness of this layer is less than the original estimated thickness. The recalibrated P-wave velocity of the hydrate layer is also higher than the original estimated velocity. For the drilling well with a relatively thin hydrate layer, the velocity ramp plays a more important role in identifying and determining the thickness of the layer.

Geochemical characteristics of cold-seep carbonates in Shenhu area,South China Sea

Cold seeps spread worldwide along the continental margins,which are closely related to the exploration of gas hydrates.Cold-seep carbonates have been reported to record the nature of seepage,including fluid source,sedimentary environment,and variation of seepage activity.We investigated the morphology,mineralogy,element compositions,and carbon and oxygen isotopes of 15 cold-seep carbonates collected from the Shenhu area,and compared them with 2 carbonates from the Haima cold seep,the South China Sea(SCS),to promote our knowledge of cold-seep system in SCS.Most of the Shenhu carbonates exhibit crust morphology,and some are in the form of chimneys and blocks.Their absolute(20%–65%)and relative carbonate mineral contents(mainly aragonite and calcite,with minor samples containing dolomite)vary significantly,indicating the multi-stage methane leakage in our study area.Some samples show a slight negative Ce anomaly,suggesting either the mixing of seawater or variation of the redox condition during the precipitation;the cooccurrence of strongly enriched U and Mo demonstrates anoxic condition during precipitation.The mixed genetic methane source was interpreted by δ^(13)C of the Shenhu carbonates to range from-22.34‰to-59.30‰Vienna PeeDee Belemnite(VPDB),and the slight ^(18)O-enrichment imprinted on the carbonates suggests the possible influence from hydrate dissociation.The Haima carbonates,with biogenic methane as the main gas source,were presumably formed in a stronger fluid flux by compared with our Shenhu samples.

Distributed optical fiber acoustic sensor for in situ monitoring of marine natural gas hydrates production for the first time in the Shenhu Area,China

The distributed acoustic sensor(DAS)uses a single optical cable as the sensing unit,which can capture the acoustic and vibration signals along the optical cable in real-time.So it is suitable for monitoring downhole production activities in the process of oil and gas development.The authors applied the DAS system in a gas production well in the South China Sea for in situ monitoring of the whole wellbore for the first time and obtained the distributed acoustic signals along the whole wellbore.These signals can clearly distinguish the vertical section,curve section,and horizontal production section.The collected acoustic signal with the frequency of approximately 50 Hz caused by the electric submersible pump exhibit a signal-to-noise ratio higher than 27 dB.By analyzing the acoustic signals in the production section,it can be located the layers with high gas production rates.Once an accurate physical model is built in the future,the gas production profile will be obtained.In addition,the DAS system can track the trajectory of downhole tools in the wellbore to guide the operation.Through the velocity analysis of the typical signals,the type of fluids in the wellbore can be distinguished.The successful application of the system provides a promising whole wellbore acoustic monitoring tool for the production of marine gas hydrate,with a good application prospect.

Assessment of natural gas hydrate reservoirs at Site GMGS3-W19 in the Shenhu area,South China Sea based on various well logs

To obtain the characteristics of the gas hydrate reservoirs at GMGS3-W19,extensive geophysical logging data and cores were analyzed to assess the reservoir properties.Sediment porosities were estimated from density,neutron,and nuclear magnetic resonance(NMR)logs.Both the resistivity and NMR logs were used to calculate gas hydrate saturations,the Simandoux model was employed to eliminate the effects of high clay content determined based on the ECS and core data.The density porosity was closely in agreement with the core-derived porosity,and the neutron porosity was higher while the NMR porosity was lower than the density porosity of sediments without hydrates.The resistivity log has higher vertical resolution than the NMR log and thus is more favorable for assessing gas hydrate saturation with strong heterogeneity.For the gas hydrate reservoirs at GMGS3-W19,the porosity,gas hydrate saturation and free gas saturation was 52.7%,42.7%and 10%,on average,respectively.The various logs provide different methods for the comprehensive evaluation of hydrate reservoir,which supports the selection of candidate site for gas hydrate production testing.

A 3D basin modeling study of the factors controlling gas hydrate accumulation in the Shenhu Area of the South China Sea

Great advancement has been made on natural gas hydrates exploration and test production in the northern South China Sea.However,there remains a lot of key questions yet to be resolved,particularly about the mechanisms and the controls of gas hydrates enrichment.Numerical simulaution would play signficant role in addressing these questions.This study focused on the gas hydrate exploration in the Shenhu Area,Northern South China Sea.Based on the newly obtained borehole and multichannel reflection seismic data,the authors conducted an integrated 3D basin modeling study on gas hydrate.The results indicate that the Shenhu Area has favorable conditions for gas hydrate accumulation,such as temperature,pressure,hydrocarbon source,and tectonic setting.Gas hydrates are most concentrated in the Late Miocene strata,particularly in the structual highs between the Baiyun Sag and the Liwan Sag,and area to the south of it.It also proved the existence of overpressure in the main sag of source rocks,which was subject to compaction disequilibrium and hydrocarbon generation.It also shown that the regional fault activity is not conducive to gas hydrate accumulation due to excess gas seepage.The authors conjecture that fault activity may slightly weaken overpressure for the positive effect of hydrocarbon expulsion and areas lacking regional fault activity have better potential.

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.

Application of frequency division inversion in the prediction of heterogeneous natural gas hydrates reservoirs in the Shenhu Area,South China Sea

Drilling results suggest that the thickness of natural gas hydrates(NGHs)in the Shenhu Area,South China Sea(SCS)are spatially heterogenous,making it difficult to accurately assess the NGHs resources in this area.In the case that free gas exists beneath hydrate deposits,the frequency of the hydrate deposits will be noticeably attenuated,with the attenuation degree mainly affected by pore development and free gas content.Therefore,the frequency can be used as an important attribute to identify hydrate reservoirs.Based on the time-frequency characteristics of deposits,this study predicted the spatial distribution of hydrates in this area using the frequency division inversion method as follows.Firstly,the support vector machine(SVM)method was employed to study the amplitude versus frequency(AVF)response based on seismic and well logging data.Afterward,the AVF response was introduced as independent information to establish the nonlinear relationship between logging data and seismic waveform.Then,the full frequency band information of the seismic data was fully utilized to obtain the results of frequency division inversion.The inversion results can effectively broaden the frequency band,reflect the NGHs distribution,and reveal the NGHs reservoirs of two types,namely the fluid migration pathway type and the in situ self-generation self-storage diffusion type.Moreover,the inversion results well coincide with the drilling results.Therefore,it is feasible to use the frequency division inversion to predict the spatial distribution of heterogeneous NGHs reservoirs,which facilitates the optimization of favorable drilling targets and is crucial to the resource potential assessment of NGHs.

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.

Variations of pore water sulfate gradients in sediments as indicator for underlying gas hydrate in Shenhu Area, the South China Sea

Shenhu Area is one of the most promising areas for gas hydrate exploration in the northern South China Sea （SCS）. Pore water sulfate gradient, sulfate-methane interface （SMI） depth, and sulfate flux were analyzed at 53 sites in this area. SO42- gradient ranges between 0.33 and 4.43 mmol L-L m-1. SMI depths are from 7.7 to 87.9 mbsf. Sulfate flux varies between 2.0 and 26.9 mmol m-2 yr L, with a mean of 11.7 mmol m-2 yr1. Correlation coefficient between SMI depth and methane flux for the 53 sites is -0.80, implying that methane flux regulates the rate of anaerobic methane oxidation （AMO）, SMI depth, and sulfate flux. Twelve anomalous fields with high methane flux and steep sulfate gradients were recognized. Bottom simulating reflector （BSR） is distributed mainly in areas where SMI depth is less than 50 mbsf or places with sulfate flux larger than 3.5 mmol m-2 yr-1. It is suggested that the Baiyun Sag and the Southern Uplift are potential areas for gas hydrate exploration.

Characteristics of authigenic pyrites in shallow core sediments in the Shenhu area of the northern South China Sea: Implications for a possible mud volcano environment

Distinct pyrites have been recovered from a shallow sediment core from Site 4B in the Shenhu area of the northern South China Sea. Based on the lithology, texture and structure of sediments, the stable sulfur isotope of pyrite and the total organic carbon (TOC) concentration of the sediments, a distinctive sediment interface is identified at a depth of about 1 m below the seafloor in the core sediments. The pyrites only accumulate in the lower part of the core as rods and foraminifera-infillings, and mainly within three intervals marked by high pyrite concentrations. The amount of pyrite in the sediments shows no remarkable correlation with TOC in the Site 4B core sediments. The stable sulfur isotopes of the pyrite have extremely negative values ranging from 41.69‰ to 49.16‰. They are considered to be the mutual product of sulfate bacterial reduction and sulfur bacterial disproportionation. Our research proposes that Site 4B might be located in or near a possible mud volcano sedimentary environment; a large amount of methane could migrate from deep to shallow sediments in an active mud volcano and thereby play a key role in the intensity of sulfate bacterial reduction and the amount of pyrite formed at Site 4B. Further, the variation in flux of deep methane fluid by intermittent mud volcanic eruptions might result in the deposition of authigenic pyrite intervals.