Numerical modeling study of mineralization induced by methane cold seep at the sea bottom

In order to investigate the response of authigenic minerals to gas hydrate geo-systems, the biogeochemical processes and its induced mineralization were predicted by employing the comprehensive reactive transport modeling approach. Based on the available data extracted from the northern continental slope area of the South China Sea, a 1-D vertical column model was developed. Three cases with different upward methane flux rates and three cases with different mineral compositions, i.e., a total of six cases were designed to investigate the effects of variations in the depth of sulfate methane transition zone (SMTZ) and in the mineral composition on the formation of authigenic minerals. The simulation results indicate that the SMTZ depth influenced by both the upward methane flux rate and the initial composition played an important role in the formation of authigenic minerals. The AOM reaction is intensive at the interface, and the precipitation amount of calcite is large, which is mainly controlled by AOM. When the methane leakage rate is 20 times higher than the base case, aragonite starts to precipitate. During the simulation, oligoclase, k-feldspar, smectite-Na, smectite-Ca, chlorite dissolved. Our study specific to this area as a starting point may provide a quantitative approach for investigating carbonate and pyrite formation in hydrate-bearing sediments accounting for methane oxidation and sulfate reduction. The method presented here and the model built in this study can be used for other sites with similar conditions. In addition, this study may serve as an indication for the potential natural gas hydrate reservoir in depth, and is also significant for marine carbon and sulfur cycle.     

Characterizing lipid biomarkers in methanotrophic communities of gas hydrate-bearing sediments in the Sea of Okhotsk

We studied specific lipid biomarkers of archaea and bacteria, that are associated with the anaerobic oxidation of methane (AOM) in a cold seep environment as well as the origin of sedimentary organic matter on the continental slope off NE Sakhalin in the Sea of Okhotsk. The organic geochemical parameters demonstrated that most of the sedimentary organic matter containing hydrate layers could be derived from marine phytoplankton and bacteria, except for a station (LV39-29H) which was remarkably affected by terrestrial vascular plant. Specific methanotrophic archaea biomarkers was vertically detected in hydrate-bearing cores (LV39-40H), coinciding with the negative excursion of the δ¹³C_org at core depths of 90–100 cm below the seafloor. These results suggest that methane provided from gas hydrates are already available substrates for microbes thriving in this sediment depth. In addition, the stable isotope mass balance method revealed that approximately 2.77–3.41% of the total organic carbon (or 0.036–0.044% dry weight sediment) was generated by the activity of the AOM consortium in the corresponding depth of core LV39-40H. On the other hand, the heavier δ¹³C values of archaeol in the gas hydrate stability zone may allow ongoing methanogenesis in deeper sediment depth.     

Pore-water geochemistry in methane-seep sediments of the Makran accretionary wedge off Pakistan: Possible link to subsurface methane hydrate

Cold seeps are pervasive along the continental margin worldwide,and are recognized as hotspots for elemental cycling pathway on Earth.In this study,analyses of pore water geochemical compositions of one-400 cm piston core(S3) and the application of a mass balance model are conducted to assess methane-associated biogeochemical reactions and uncover the relationship of methane in shallow sediment with gas hydrate reservoir at the Makran accretionary wedge off Pakistan.The results revealed that approximately 77% of sulfate is consumed by the predominant biogeochemical process of anaerobic oxidation of methane.However,the estimated sulfate-methane interface depth is-400 cm below sea floor with the methane diffusive flux of 0.039 mol/(m~2·a),suggesting the activity of methane seepage.Based on the δ~(13)C_(DIC) mass balance model combined with the contribution proportion of different dissolved inorganic carbon sources,this study calculated the δ~(13)C of the exogenous methane to be-57.9‰,indicating that the exogenous methane may be a mixture source,including thermogenic and biogenic methane.The study of pore water geochemistry at Makran accretionary wedge off Pakistan may have considerable implications for understanding the specific details on the dynamics of methane in cold seeps and provide important evidence for the potential occurrence of subsurface gas hydrate in this area.     

Methane hydrate recycling offshore of Mauritania probably after the last glacial maximum

To what extent methane liberated from marine hydrate will enter the ocean during a warmer world is unknown. Although methane release due to hydrate dissociation has been modelled, it is unclear whether or not methane will reach the seafloor during a warmer world and therefore contribute to oceanic and atmospheric budgets. Here we show, using a new three-dimensional (3-D) seismic dataset, that some hydrate deposits surround the gas chimneys passing through the HSZ. Bottom water warming since the last glacial maximum (LGM) is interpreted to cause hydrate dissociation but critically some of the released methane was not vented to the ocean. The released gas caused seal failure and free gas entered the hydrate stability zone (HSZ) through vertical gas chimneys to where new hydrate accumulations formed. This process is a new evidence for methane recycling and could account in part for the lack of methane in ice core records that cover warming events during the late Quaternary. This research provides new insight into how methane could be recycled rather than vented during a warmer world.     

九龙江河口沉积物中硫酸盐还原与甲烷厌氧氧化:同位素地球化学证据

通过沉积物柱孔隙水中甲烷,SO2-4,Cl-,δc(34S-SO2-4)、δc(13 C-CH4)的垂直分布特征,研究了硫酸盐还原和甲烷厌氧氧化(anaerobic oxidation of methane,简称AOM)过程在九龙江河口沉积物中的分布规律.测定结果显示两个站位(J-A和J-E)间隙水中SO2-4浓度随深...     

Structural controls on the formation of BSR over a diapiric anticline from a dense MCS survey offshore southwestern Taiwan

A dense seismic reflection survey with up to 250-m line-spacing has been conducted in a 15 × 15 km wide area offshore southwestern Taiwan where Bottom Simulating Reflector is highly concentrated and geochemical signals for the presence of gas hydrate are strong. A complex interplay between north–south trending thrust faults and northwest–southeast oblique ramps exists in this region, leading to the formation of 3 plunging anticlines arranged in a relay pattern. Landward in the slope basin, a north–south trending diapiric fold, accompanied by bright reflections and numerous diffractions on the seismic profiles, extends across the entire survey area. This fold is bounded to the west by a minor east-verging back-thrust and assumes a symmetric shape, except at the northern and southern edges of this area, where it actively overrides the anticlines along a west-verging thrust, forming a duplex structure. A clear BSR is observed along 67% of the acquired profiles. The BSR is almost continuous in the slope basin but poorly imaged near the crest of the anticlines. Local geothermal gradient values estimated from BSR sub-bottom depths are low along the western limb and crest of the anticlines ranging from 40 to 50 °C/km, increase toward 50–60 °C/km in the slope basin and 55–65 °C/km along the diapiric fold, and reach maximum values of 70 °C/km at the southern tip of the Good Weather Ridge. Furthermore, the local dips of BSR and sedimentary strata that crosscut the BSR at intersections of any 2 seismic profiles have been computed. The stratigraphic dips indicated a dominant east–west shortening in the study area, but strata near the crest of the plunging anticlines generally strike to southwest almost perpendicular to the direction of plate convergence. The intensity of the estimated bedding-guided fluid and gas flux into the hydrate stability zone is weaker than 2 in the slope basin and the south-central half of the diapiric fold, increases to 7 in the northern half of the diapiric fold and plunging anticlines, and reaches a maximum of 16 at the western frontal thrust system. Rapid sedimentation, active tectonics and fluid migration paths with significant dissolved gas content impact on the mechanism for BSR formation and gas hydrate accumulation. As we begin to integrate the results from these studies, we are able to outline the regional variations, and discuss the importance of structural controls in the mechanisms leading to the gas hydrate emplacements.     

Effects of dissociation on the shear strength and deformation behavior of methane hydrate-bearing sediments

A series of tests were conducted in order to investigate the shear strength and deformation behavior of methane hydrate-bearing sediments during dissociation using the thermal recovery method or depressurization method. An innovative temperature-controlled high pressure triaxial apparatus which can reproduce the in situ conditions of hydrate reservoirs was used. The results indicate that: (1) the failure strength of isotropically consolidated methane hydrate-bearing sediments which dissociated completely using the thermal recovery method is less than that of pure Toyoura sand. However, the initial stiffness and volumetric strain are higher than that of pure Toyoura sand. (2) The thermal recovery method will cause the failure of methane hydrate-bearing sediments when the axial load is higher than the strength of methane hydrate-bearing sediments after dissociation. (3) The depressurization method will not cause collapse of methane hydrate-bearing sediments during depressurization. However, water pressure recovery will lead to failure when the axial load is larger than the strength of the methane hydrate-bearing sediments after dissociation. (4) The depressurization rate shows little effect on the ultimate deformation of methane hydrate-bearing sediments, while the initial deformation rate increases with increasing depressurization rate. (5) The larger the reduction of pore pressure, the larger axial strain and volumetric strain.     

Canyon-infilling and gas hydrate occurrences in the frontal fold of the offshore accretionary wedge off southern Taiwan

We utilized reflection seismic and bathymetric data to infer the canyon-infilling, fold uplift, and gas hydrate occurrences beneath the frontal fold at the toe of the accretionary wedge, offshore SW Taiwan. The lateral migrating paleo-Penghu canyons has cut across the frontal fold with six distinct canyon/channel incisions marked by channel infills. The longitudinal bathymetric profile along the modern canyon course shows a knickpoint of ~300 m relief at this frontal fold, indicating that the rate of fold uplift is greater than that of canyon incision. The age for the initial thrusting of this fontal fold is around 240 kyr ago, as estimated by using the maximum thickness of growth strata of this fold divided by the sedimentation rate obtained from a nearby giant piston core. Bottom simulating reflector (BSR) on seismic sections indicates the base of gas hydrate stability zone. Beneath the frontal fold, there is a widespread occurrence of BSRs, suggesting the highly probable existence of substantial quantities of gas hydrates. A seismic flat spot and a few push-down reflectors below BSR are found lying beneath the anticlinal axis with bathymetric four-way dip closure. The flat spot, cutting across a series of dipping reflections beneath BSR, may indicate the contact between free gas and its underlying formation water. The push-down reflectors beneath BSRs are interpreted to result from abundant free gas hosted beneath the gas hydrate stability zone. The multiple paleo-canyon infills seen along and beneath the frontal fold and above BSRs may provide thick porous sands to host gas hydrates in the frontal fold.     

南海东沙东北部甲烷缺氧氧化作用的生物标志化合物及其碳同位素组成

南海东沙东北部碳酸盐岩和泥质沉积物中的生物标志化合物组合及其碳同位素组成分析表明,研究区内甲烷缺氧氧化作用(anaerobic oxidation of methane-AOM)发育.研究区内碳酸盐岩中含丰富的AOM标志化合物,2,6,11,15-四甲基十六烷(Crocetane-Cr.)、2,6,10,15,19-五甲基番茄烷(Pentamethylicosane-PMI)和2,6,10,15,19,23-六甲基二十四烷(Squalane-Sq角鲨烷)的13C亏损强烈(δ13C值介于-74.2‰~-119.0‰PDB之间),表明碳酸盐岩形成于AOM,同时反映该研究区曾发生过强烈、持续的富CH₄流体释放活动.柱状泥质沉积物中,AOM生物标志化合物在硫酸岩-甲烷过渡带(SMI-Sulfate-Methane Interface)边界附近相对丰度高,SMI之上样品中含量低,或未检出,表明现代环境在SMI附近有大量嗜甲烷微生物生长,使得深部上升的甲烷被大量消耗,很少有甲烷逸出海底.AOM生物标志化合物可用来指示SMI边界.不同站位、不同岩性AOM生物标志化合物组成(包括碳同位素组成)的差异反映了嗜甲烷古细菌组成的不同.     

Experimental studies on the possible influences of composition changes of pore water on the stability conditions of methane hydrate in marine sediments

Experiments with a set of electrolyte solutions have been carried out to investigate the effects of pore water composition changes on the stability conditions of methane hydrate in marine sediments. The results reveal that (1) SO₄²⁻ and Cl⁻ concentration changes can affect hydrate stability slightly, (2) the changes in both the type and the concentration of cations, which occur in normal diagenetic processes, do not exert a significant influence on the methane hydrate stability conditions, and (3) the shift of hydrate stability in pore water can be expressed as a function of the Cl⁻ concentration only. Based on the results above, an empirical equation ΔT (K)=0.00206 Cl⁻ (mmol/dm³) has been obtained for estimating the shift in the equilibrium temperature of methane hydrate in pore water at a given pressure.     

Effective medium modeling to assess gas hydrate and free-gas evident from the velocity structure in the Makran accretionary prism, offshore Pakistan

Seismic properties of sediments are strongly influenced by pore fluids. Stiffness of unconsolidated marine sediment increases with the presence of gas hydrate and decreases with the presence of gas. A strong bottom-simulating reflector (BSR) observed on a seismic profile in the Makran accretionary prism, offshore Pakistan, indicates the presence of gas hydrate and free-gas across the BSR. Elastic properties of gas depend largely on pressure and temperature. We, therefore, first determine the elastic modulus of gas at pressure and temperature calculated at the BSR depth in the study region. The interval velocities derived from the seismic data are interpreted by the effective medium theory, which is a combination of self-consistent approximation and differential effective medium theories, together with a smoothing approximation, for assessment of gas hydrate and free-gas. The results show the saturations of gas hydrate and free-gas as 22 and 2.4% of pore space, respectively, across the BSR.     

Particle size effect on the saturation of methane hydrate in sediments – Constrained from experimental results

Except for those occurring at seafloor, most of natural gas hydrate form in sediments and are subject to the influence of sediment. Among these factors, the particle size effect on hydrate saturation level in sediment have been studied with a series of silica sands with various sizes, and the results obtained clearly indicate that particle size does play an important role in affecting the saturation level of hydrate in sediments. The proton relaxation times of water confined in the same series of silica sands, which were determined with NMR measurement, show logarithmic relationship with particle size. By comprehensive consideration of the results of hydrate saturation and water proton relaxation times, the particle size effect observed is tentatively explained by the water availability for hydrate formation in sediments.     

Analysis of formation pressure test results in the Mount Elbert methane hydrate reservoir through numerical simulation

Targeting the methane hydrate (MH) bearing units C and D at the Mount Elbert prospect on the Alaska North Slope, four MDT (Modular Dynamic Formation Tester) tests were conducted in February 2007. The C2 MDT test was selected for history matching simulation in the MH Simulator Code Comparison Study. Through history matching simulation, the physical and chemical properties of the unit C were adjusted, which suggested the most likely reservoir properties of this unit. Based on these properties thus tuned, the numerical models replicating “Mount Elbert C2 zone like reservoir”, “PBU L-Pad like reservoir” and “PBU L-Pad down dip like reservoir” were constructed. The long term production performances of wells in these reservoirs were then forecasted assuming the MH dissociation and production by the methods of depressurization, combination of depressurization and wellbore heating, and hot water huff and puff. The predicted cumulative gas production ranges from 2.16 × 10⁶ m³/well to 8.22 × 10⁸ m³/well depending mainly on the initial temperature of the reservoir and on the production method.This paper describes the details of modeling and history matching simulation. This paper also presents the results of the examinations on the effects of reservoir properties on MH dissociation and production performances under the application of the depressurization and thermal methods.     

Potential map of gas hydrate formation in Caspian Sea based on physicochemical stability evaluation of methane hydrate

Preliminary studies of Caspian Sea have shown the possibility of gas hydrate accumulations, because of suitable physicochemical conditions, existence of clayey deposits, and high concentrations of organic matter. Studies have indicated that gas hydrates are mainly composed of methane. Therefore, based on physicochemical equations for methane hydrate stability in different pressure, temperature, and salinity, this study was designed to calculate the potential of gas hydrate formation in the Caspian Sea basin. For this, data of more than 600 locations were analyzed and in each location, upper and lower limits of methane hydrate formation zone were calculated. Then, the zoning maps of upper and lower limits were prepared which can be useful for exploring the gas hydrate as an energy source or predicting gas hydrate hazards. According to the calculations and maps, methane hydrate formation in Caspian Sea, theoretically, can take place from near the seabed to 4000 and 2500 m beneath the sea surface when low and high geothermal gradient are supposed, respectively. By comparing the results with gas hydrate zones revealed in geophysical profiles, it has been shown that, in Caspian Sea, gas hydrates probably accumulate near the lower limit when a high geothermal gradient is assumed.     

Using sediment geochemistry to infer temporal variation of methane flux at a cold seep in the South China Sea

Release of methane from the seafloor throughout the world's oceans and the biogeochemical processes involved may have significant effects on the marine sedimentary environment. Identification of such methane release events in marine sediment records can hence provide a window into the magnitude of ancient seeps. Here, we report on analysis of the geochemical composition of samples in a 12.3 m long sediment core (DH-5) collected from a seep site in the South China Sea (SCS). Our aim has been to investigate whether the evidence for the presence of methane release event within sediments is discernible from solid-phase sediment geochemistry. We show that sedimentary total sulfur (TS), δ³⁴S values of chromium reducible sulfur (δ³⁴S_CRS) along with total organic carbon (TOC) and total inorganic carbon (TIC) content can be used to infer the presence of methane release events in cold seep settings. At least three methane release events were identified in the studied core (Unit I at 400–550 cm, Unit II at 740–820 cm, and Unit III at 1000–1150 cm). According to the characteristic of redox-sensitive elements (eg., Mo, U and Mn), we suggest that methane flux has been changed from relatively high (Unit I) to low (Unit II and III) rates. This inference is supported by the coupled occurrence of ³⁴S-enriched sulfides in Unit II and III. AMS ¹⁴C dates from planktonic foraminifera in Unit I suggest that high methane flux event occurred at ∼15.4–24.8 kyr BP, which probably resulted in locally-focused aerobic methane oxidation. Overall, our results suggest that TS, TOC, TIC and δ³⁴S_CRS have potential for identifying present and fossil methane release events in marine sediments.     

Geotechnical properties of deep oceanic sediments recovered from the hydrate occurrence regions in the Ulleung Basin, East Sea, offshore Korea

This study presents comprehensive geotechnical data of the natural marine sediments cored from the hydrate occurrence regions during the Ulleung Basin Gas Hydrate Expedition 1 (UBGH1), East Sea, offshore Korea in 2007. Geotechnical soil index properties of the Ulleung Basin sediments, including grain size distribution, porosity, water content, Atterberg limits, specific gravity, and specific surface area, were experimentally determined. These soil index properties were correlated to geotechnical engineering parameters (e.g., shear strength and friction angle) by using well-known empirical relationships. By performing standard consolidation tests on both undisturbed specimens (as recovered from the original core liner after hydrate dissociation) and remolded specimens, stress-dependent mechanical and hydraulic properties (e.g., compressibility and hydraulic conductivity) were measured. The experimental results provide important engineering parameters, and demonstrate the effect of hydrate presence and consequential dissociation to index properties, engineering parameters, and innate sediment structures.     

The structure of methane gas hydrate bearing sediments from the Krishna-Godavari Basin as seen from Micro-CT scanning

The Indian National Gas Hydrate Program (NGHP) Expedition 1, of 2006, cored through several methane gas hydrate deposits on the continental shelf around the coast of India. The pressure coring techniques utilized during the expedition (HYACINTH and PCS) enabled recovery of gas hydrate bearing, fine-grained, sediment cores to the surface. After initial characterization core sections were rapidly depressurized and submerged in liquid nitrogen, preserving the structure and form of the hydrate within the host sediment. Once on shore, high resolution X-ray CT scanning was employed to obtain detailed three-dimensional images of the internal structure of the gas hydrate. Using a resolution of 80 μm the detailed structure of the hydrate veins present in each core could be observed, and allowed for an in depth analysis of orientation, width and persistence of each vein. Hydrate saturation estimates could also be made and saturations of 20-30% were found to be the average across the core section with some portions showing highs of almost 60% saturation. The majority of hydrate veins in each core section were found to be orientated between 50 and 80° to the horizontal. Analysis of the strikes of the veins suggested a slight preferential orientation in individual sample sections, although correlation between individual sections was not possible due to the initial orientation of the sections being lost during the sampling stage. The preferred vein orientation within sample sections coupled with several geometric features identified in individual veins, suggest that hydraulic fracturing by upward advecting pore fluids is the main formation mechanism for the veined hydrate deposits in the K-G Basin.     

南海南部浅表层柱状沉积物孔隙水地球化学特征对甲烷渗漏活动的指示

海底沉积物孔隙水地球化学特征能快速响应甲烷渗漏活动及其生物地球化学过程,从而记录甲烷渗漏活动特征。对采自南海南部北康盆地的3个重力沉积柱状沉积物孔隙水样品（BH-H75、BH-H13Y和BH-H61）进行了甲烷浓度、溶解无机碳（DIC）和碳同位素（δ13CDIC）、阴离子（SO42−、Cl−）以及主微量元素（Ca2+、Mg2+、Sr2+、Ba2+）等地球化学分析。（△DIC+△Ca2++△Mg2+）/△SO42−比率图解与δ13CDIC深度剖面特征揭示了有机质硫酸盐还原反应（OSR）和硫酸盐驱动-甲烷厌氧氧化反应（SD-AOM）在不同沉积柱中所占比例的不同,其中BH-H13Y沉积柱中OSR和SD-AOM共同存在;BH-H75沉积柱中OSR占主导;在BH-H61沉积柱中SD-AOM占主导,且其底部可能存在微生物产甲烷作用。硫酸盐浓度线性拟合关系指示BH-H13Y的硫酸盐-甲烷过渡带（SMTZ）的深度约为700 cmbsf。结合SO42−浓度、DIC浓度最大值和δ13CDIC最小值推测BH-H61的SMTZ深度约为480 cmbsf。BH-H61和BH-H13Y沉积柱中,较浅的SMTZ深度、上升的DIC浓度以及强烈负偏的δ13CDIC值指示研究区存在甲烷渗漏活动。此外,在BH-H61和BH-H13Y站位,硫酸盐浓度随深度降低的变化梯度在沉积柱下部较上部陡,指示向上迁移的甲烷通量在时间上逐渐增强。孔隙水中Ca2+、Mg2+、Sr2+浓度以及Mg/Ca、Sr/Ca比值变化特征指示研究区沉积物中可能有自生高镁方解石矿物生成;而BH-H61站位SMTZ界面以下,孔隙水中Ba2+浓度升高,指示了硫酸钡的溶解作用。     

珠江口淇澳岛海岸带沉积物中硫酸盐还原和不同形态硫的分布

对珠江口淇澳岛海岸带3个站位(QA-11,QA-9和QA-14)的沉积物中不同形态的还原硫(酸可挥发性硫,黄铁矿和有机硫)、总有机碳(TOC)和孔隙水中SO42-,甲烷浓度进行了测定,并且利用稳态扩散模型计算其中2个站位(QA-9和QA-14)硫酸盐还原通量[1.74和1.14 mmol/(m2.d)]和甲烷厌氧氧化通量[0.34和0.29 mmol/(m2.d)]。研究结果表明由于潮间带沉积物受到SO42-供给的限制,因此位于潮间带的QA-11站位硫酸盐还原带较浅(约16 cm);在潮下带的QA-9和QA-14站位,随离海岸距离和水深的增加,硫酸盐还原通量呈现减小的趋势,并且硫酸还原逐渐受到可利用活性有机质的限制;甲烷厌氧氧化对硫酸盐还原的贡献表现出增加的趋势,由19.2%增加至25.5%。三个站位沉积物中按不同形态还原硫含量由大到小列出,它们是有机硫(OS)、黄铁矿(DS)、酸可挥发性硫(AVS)。沉积物中AVS的空间分布与硫酸盐还原通量有正相关性。QA-11和QA-14站位的黄铁矿与AVS硫的含量比值大于3,分别为7.9和3.6,表明两个站位的黄铁矿形成可能受硫酸盐还原作用的控制;QA-9站位黄铁矿与AVS硫的含量比值为2.2,暗示AVS向黄铁矿转化受到可利用活性铁的限制。     

南海北部陆坡沉积物硫酸盐-甲烷反应界面深度的空间变化及其对甲烷水合物赋存状态差异性的指示意义

海洋沉积物中的硫酸盐-甲烷反应界面（SMI）的深度变化能够指示下伏甲烷水合物的赋存状态。本文通过对南海北部陆坡天然气水合物潜在分布区沉积物间隙水化学和自生碳酸盐氧、碳同位素组成资料系统分析和对比,探讨了南海北部陆坡沉积物的SMI深度空间变化对下伏甲烷水合物的赋存状态的指示意义。结果表明,南海北部陆坡沉积物的SMI的深度呈现出从西南-东北变浅的趋势,这一趋势与自生碳酸盐的碳同位素组成揭示的甲烷释放量增大趋势有很好的对应关系,进而表明在南海北部陆坡从西南-东北甲烷水合物的埋藏深度变浅或者甲烷水合物的分解程度增大。