Halogen systematics in the Mallik 5L-38 gas hydrate production research well,Northwest Territories,Canada: Implications for the origin of gas hydrates under terrestrial permafrost conditions

The authors report here halogen concentrations in pore waters and sediments collected from the Mallik 5L-38 gas hydrate production research well, a permafrost location in the Mackenzie Delta, Northwest Territories, Canada. Iodine and Br are commonly enriched in waters associated with CH₄, reflecting the close association between these halogens and source organic materials. Pore waters collected from the Mallik well show I enrichment, by one order of magnitude above that of seawater, particularly in sandy layers below the gas hydrate stability zone (GHSZ). Although Cl and Br concentrations increase with depth similar to the I profile, they remain below seawater values. The increase in I concentrations observed below the GHSZ suggests that I-rich fluids responsible for the accumulation of CH₄ in gas hydrates are preferentially transported through the sandy permeable layers below the GHSZ. The Br and I concentrations and I/Br ratios in Mallik are considerably lower than those in marine gas hydrate locations, demonstrating a terrestrial nature for the organic materials responsible for the CH₄ at the Mallik site. Halogen systematics in Mallik suggest that they are the result of mixing between seawater, freshwater and an I-rich source fluid. The comparison between I/Br ratios in pore waters and sediments speaks against the origin of the source fluids within the host formations of gas hydrates, a finding compatible with the results from a limited set of ¹²⁹I/I ratios determined in pore waters, which gives a minimum age of 29 Ma for the source material, i.e. at the lower end of the age range of the host formations. The likely scenario for the gas hydrate formation in Mallik is the derivation of CH₄ together with I from the terrestrial source materials in formations other than the host layers through sandy permeable layers into the present gas hydrate zones.     

Terrestrial organic matter controlling gas hydrate formation in the Nankai Trough accretionary prism, offshore Shikoku, Japan

Sediment core samples from Sites 1175, 1176, and 1178, ODP Leg 190, Nankai Trough were analyzed for sedimentary organic matter and inorganic elemental compositions to clarify geochemical conditions for the formation of gas hydrate. Low chloride concentrations and anomalously low core temperature infer the existence of gas hydrate at Site 1178. Trace amounts of gas hydrate are also suggested for Site 1176. Site 1175 does not have any significant evidence of gas hydrate, although all the three sites are within the gas hydrate stability zone. The sediment from Site 1178 is characterized by abundant terrigenous organic matter, older geologic ages, and comparatively higher maturity levels, suggesting high rates of CO₂ generation during diagenesis. The CO₂ generation potential of sediment may be one of the crucial conditions for the formation of gas hydrate.     

Archaeal polar lipids in subseafloor sediments from the Nankai Trough: Implications for the distribution of methanogens in the deep marine subsurface

Although the methane in marine methane hydrates is mainly of microbial origin, information about the distribution of methanogens in subseafloor sediments is limited. To address this issue, we analyzed sediment core samples from two sites in the Nankai Trough, off the Pacific coast of central Japan, including those bearing methane hydrates from depths > 100 m below the seafloor (mbsf), for isopranyl ether-linked polar lipids (i.e. with polar head groups of phosphate, sugar, or both) as biomarkers of archaea, including methanogens. In most samples, including the deepest (381 mbsf), archaeol, and sn-2- and sn-3-hydroxyarchaeols were detected as their hydrolyzed derivatives. Concentrations of these three archaeal lipids correlated strongly with each other, suggesting a common biological source. The δ¹³C values of phytane derived from the phytanyl groups in the archaeal lipids were distinctly higher than those of methane, indicating that methanogens rather than anaerobic methanotrophic archaea were the major biological source. Depth profiles of polar sn-2-hydroxyarchaeol concentration were consistent with those of the potential methane production activity previously estimated from incubation of core sediments from the same sites. This observation, together with results of previous studies showing the presence of sn-2-hydroxyarchaeol mainly in shallow young sediments, strongly suggests that this polar lipid is a valid biomarker for in situ methanogens in sediments. There was a strong correlation between the concentration of polar sn-2-hydroxyarchaeol and that of total organic carbon, suggesting that bulk organic matter concentration is a primary control on the distribution of methanogens in sediments.     

Characteristics of Intraslab Stress Field and Tectonic Implication in the Nankai Trough, Japan

1. IntroductionThe Nankai Trough region (Fig. 1.1) of southwest Japan is one of the most tectonically complex subduction zones in the world. The subduction of the Philippine Sea plate (PH) beneath the Eurasian plate (EU) has caused a series of large and great interplate earthquakes. It is generally accepted that great earthquakes have occurred at intervals of 100-150 years along the Nankai subduction zone since the 684 Hakuho earthquake (Fig. 1.2). However, a large earthquake (M>7.5) has…     

日本南海海槽俯冲增生楔前缘的构造变形特征

对增生楔不同压力—温度条件下的构造变形、流体活动、沉积特征、岩石物性和化学组成等多方面的直接观测,可以帮助分析俯冲带地震的蕴育和发生的环境与机理。通过参加IODP的日本南海海槽发震带研究项目(NanTroSEIZE)第一阶段316航次所收集到的大量第一手数据和资料,分别在4个站位上(C0004,C0006,C0007,C0008)对日本南海海槽增生楔前缘岩芯尺度上的构造变形进行了详细分析,并且讨论了岩芯尺度上的构造变形与增生楔中大尺度的非序列分支逆冲断层和前缘逆冲断层的构造变形之间的关系。发现逆冲变形不是只在大尺度的逆冲断层面上进行,而是弥散分布在主逆冲断层面、次级逆冲断层面以及断层面之间的更小的尺度上。小尺度构造的倾向与大尺度断层的倾向有较好的一致性,表明它们是在相同的应力场下所形成的。在增生楔浅部高角度的正断层比较发育,显示张性应力场特征,同时所获得的岩芯尺度上的地层倾角较大并倾向与反射地震以及区域地质分析结果非常吻合,而在深部,特别是在大尺度逆冲断层发育带附近,各种类型的断层、滑移变形带、节理等非常普遍,同时层理与劈理的产状的复杂变化更多地受控于复杂的逆冲断层带的作用。     

Occurrence of Free-Gas Associated with Methane-Hydrate-Bearing Formations in the MITI Nankai Trough Wells, Offshore Tokai, Japan

Abstract. The MITI Nankai Trough wells were drilled for exploration of methane-hydrate-bearing sediments in association with seismic inferred bottom simulating reflectors (BSRs). In this project, log data showed low velocity compressional-wave (P-wave) layers below methane-hydrate-bearing formations. Dipole shear sonic acoustic tools (DSI) could not acquire accurate compres-sional velocity in this zone, thus it was not possible to accurately correlate between logging, VSP and surface seismic profiles.
Small amount of gas was presumed to cause the problem in obtaining the low velocity P-wave data. VSP interval velocity data was used to assess the DSI inferred low-velocity layer, which showed lower values than the velocity of the drilling muds. Synthetic seismogram was created by VSP-compensated velocity to compare against corridor stack of VSP. As a result, the depths above and below the methane-hydrate-bearing interval were correlated with synthetic seismograms and reflectivity events on the VSP profiles. By using this correlation technique, distribution of methane-hydrate-bearing formations and free-gas-bearing formations can be determined.     

论河北丰宁牛圈银（金）矿床的成矿时限问题

南沙海槽的构造和沉积受控于南海的构造运动和加里曼丹西北大陆边缘的演化,具有适于天然气水合物形成的物源基础、温压条件、输导系统和储藏场所。似海底反射层(BSR)出现在水深650~2 800 m、海底下65~350 m深的晚中新世沉积物中,与褶皱、逆冲推覆构造及穹窿构造有关;沉积物中的甲烷含量和孔隙水的SO24-含量表现出异常变化特征,硫酸盐-甲烷界面(SMI)深度仅为8~11 m;表层沉积的自生石膏和黄铁矿的成岩环境与甲烷流体排溢引起的厌氧甲烷氧化(AOM)有关,这些地球物理和地球化学指标均指示南沙海槽发育天然气水合物。研究表明,南沙海槽沉积物的甲烷以二氧化碳还原型微生物成因为主,少量为混合气,海槽东南部可能是最有潜力的天然气水合物远景区。     

Rare earth elements in pore waters of marine sediments

The rare earth elements (REEs) were measured in pore waters of the upper ∼25 cm of sediment from one site off Peru and three sites on the California margin. The pore water REE concentrations are higher than sea water and show systematic down core variations in both concentration and normalized pattern. From these analyses and from comparison to other chemical species measured (dissolved Fe, Mn, Ba, oxygen, nitrate, phosphate), it is suggested that pore water REEs can be grouped into three categories: those that are from an Fe-source, those that are from a POC-source, and cerium oxide. REEs from the Fe-source appear where anoxia is reached; they have a distinctive “middle-REE (MREE) enriched” pattern. The concentrations in this source are so elevated that they dominate REE trends in the Fe-oxide reduction zone. The net result of flux from the POC-source is relative enrichment of heavy-REEs (HREEs) over light-REEs (LREEs), reflecting remineralizing POC and complexation with DOC. A common “linear” REE pattern, seen in both oxic and anoxic sediments, is associated with this POC-source, as well as a “HREE enriched” pattern that is seen in surficial sediments at the Peru site. Overall, the pore water results indicate that Mn-oxides are not an important carrier of REEs in the oceans.A REE biogeochemical model is presented which attempts to reconcile REE behavior in the water and sediment columns of the oceans. The model proposes that POC, Fe-oxide and Ce-oxide sources can explain the REE concentration profiles and relative abundance patterns in environments ranging from oxic sea water to anoxic pore water. The model is also consistent with our observation that the “Ce-anomaly” of pore water does not exceed unity under any redox condition.     

含天然气水合物沉积物相平衡问题研究综述

天然气水合物是一种战略性替代能源。同时,开发天然气水合物将是全球气候环境问题和地质灾害的诱发因素之一。含天然气水合物沉积物（简称HBS）的相平衡问题对天然气水合物资源勘探、评估与开发利用以及环境影响均具有重要的基础作用。自然界中赋存于沉积物之中的天然气水合物的生成与分解与纯水体系中水合物的生成与分解具有很大区别。通过总结国内外研究资料,以天然气水合物开发利用中的岩土工程问题研究需要为出发点,详细介绍了HBS的沉积物物性、孔隙水盐度和气体组分对沉积物中水合物相平衡关系影响以及HBS相平衡研究中有关制样方法技术、各组分含量测试以及相平衡关系理论模型研究方面的国内外研究现状。研究成果表明,HBS的沉积物物性、孔隙水盐度和气体组分均对天然气水合物相平衡关系具有显著影响,试验研究中应用了很多先进方法技术,但仍然存在定量精度较低或实施成本较高等问题;基于微观尺度建立的有关HBS的相平衡宏观模型能较好地模拟与预测HBS的相平衡关系,但其表达式复杂、参数较多和不易获得制约了其在天然气水合物开采中的有关岩土力学与工程理论研究和工程实践中应用     

Polar and neutral isopranyl glycerol ether lipids as biomarkers of archaea in near-surface sediments from the Nankai Trough

The molecular and carbon isotopic compositions of polar isopranyl glycerol ether lipids, which are direct indicators of viable archaea, and neutral isopranyl glycerol ether lipids, which are derived from polar lipids via hydrolysis, in near-surface sediments from a methane seep in the Nankai Trough (off central Japan) were investigated. Procedures for extracting, separating and derivatizing polar and neutral ether lipids for detection using gas chromatography were first examined with one sediment sample and a cultivated methanogen. For all sediment samples, archaeol and hydroxyarchaeol were detected in both the polar and neutral ether lipid fractions. Acyclic and cyclic biphytanes were also detected in both types of lipid fractions after treatment with HI/LiAlH₄ for ether cleavage and alkylation. The δ¹³C values of archaeol, sn-2-hydroxyarchaeol, and sn-3-hydroxyarchaeol in the sample from 0.82 m below the seafloor were lower than −100‰ relative to PDB, indicating that diverse living methanotrophic archaea are present in the seep sediments. Biphytanes released from polar ether lipids in the same sample were less depleted in δ¹³C (−71‰ to −36‰). The wide range of δ¹³C values suggests that the biphytanes were derived not only from methanotrophic but also from non-methanotrophic archaea, and that the relative contributions of the methanotrophic and non-methanotrophic archaea differed, depending on the biphytane compound. The vertical profiles and δ¹³C values of the neutral ether lipids were similar to those of the intact polar ether lipids, suggesting that neutral ether lipids derived from fossil archaea in the samples had mainly been lost by the time of sampling.     

A geothermal method for detecting gas hydrates in the bottom sediments of water basins

We formulate the fundamentals of the geothermal method for determining the hydrate saturation of bottom sediments. According to laboratory experiments (A.A. Trofimuk Institute of Petroleum Geology and Geophysics, A.V. Nikolaev Institute of Inorganic Chemistry), detecting gas hydrates in bottom sediments requires measurement of thermal conductivity at least twice at one bottom site, using a cylindrical probe with different heater power values. Changing the latter permits controlling gas hydrate stability and instability. A low-power probe does not destroy gas hydrates and permits measuring the true thermal conductivity of the sediments. Increasing heater power destroys gas hydrates near the probe and drastically increases effective thermal conductivity. Comparison between true and effective thermal conductivity clearly shows the presence of gas hydrates in the sample or their absence from it. A technique was proposed for the quantitative interpretation of changes in the temperature field of a cylindrical probe. It permits quite a precise determination of the mass of gas hydrate that decomposed in the layer surrounding the probe over a certain period. Also, it permits a rough estimation of the gas hydrate content of the sediments. Thermal conductivity can be measured in the field with submersible multichannel thermoprobes, which are commonly used for studying the heat flow through the bottom of water basins. Now it is important to perform field experiments, so that we gain the necessary experience with the geothermal method.     

Real-time drilling mud gas monitoring for qualitative evaluation of hydrocarbon gas composition during deep sea drilling in the Nankai Trough Kumano Basin

Background

Riverine particles undergo a rapid transformation when they reach estuaries. The rapid succession of hydrodynamic and biogeochemical regimes forces the particles to flocculate, settle and enter the sediment pool. The rates and magnitudes of flocculation depend on the nature of the particles which are primarily affected by the types and quantities of organic matter (OM). Meanwhile, the OM characteristics vary widely between environments, as well as within a single environment due to seasonal climate and land use variability. We investigated the effect of the OM types and quantities through laboratory experiments using natural estuarine particles from the Mississippi Sound and Atchafalaya Bay as well as model mixtures of montmorillonite and organic molecules (i.e., biopolymers (guar/xanthan gums) and humic acid).

Results

Biopolymers promote flocculation but the magnitude depends on the types and quantities. Nonionic guar gum yields much larger flocs than anionic xanthan gum, while both of them exhibit a nonlinear behavior in which the flocculation is the most pronounced at the intermediate OM loading. Moreover, the effect of guar gum is independent of salinity whereas the effect of xanthan gum is pronounced at higher salinity. Meanwhile, humic acid does not affect flocculation at all salinity values tested in this study. These results are echoed in the laboratory manipulation of the natural estuarine particles. Flocculation of the humic acid-rich Mississippi Sound particles is unaffected by the OM, whereas that of biopolymer-rich Atchafalaya Bay particles is enhanced by the OM.

Conclusions

Flocculation is positively influenced by the presence of biopolymers that are produced as the result of marine primary production. Meanwhile, humic acid, which is abundant in the rivers that drain the agricultural soils of Southeastern United States, has little influence on flocculation. Thus, it is expected that humic acid-poor riverine particles (e.g., Mississippi River, and Atchafalaya River, to a lesser degree) may be prone to rapid flocculation and settling in the immediate vicinity of the river mouths when mixed with biopolymer-rich coastal waters. It is also expected that humic acid-rich riverine particles (e.g., Pearl River) may resist immediate flocculation and be transported further away from the river mouth.     

Dissolved Al in sediments and waters of the East China Sea: Implications for authigenic mineral formation

Numerous previous studies indicate that several different authigenic aluminosilicates form in the oceans. In this study we show, using dissolved Al distributions in sediments and waters from the nearshore regions of the East China Sea, that the process of aluminosilicate formation probably begins rapidly upon contact of detrital clays with seawater. Statistical analyses of dissolved Al-Si-H⁺ relations in surface sediments indicate that the minerals forming in East China Sea sediments low in dissolved Fe are dioctahedral chlorites with an average composition EX_0.91Mg_0.77Al_5.0Si_2.7O₁₀(OH)₈ (where EX = exchangeable + 1 cation). This composition is also consistent with dissolved Al and Si measurements as a function of salinity in turbid overlying waters. Results suggest a dissolution—reprecipitation mechanism for clay mineral reconstitution. This mechanism can help to explain why different authigenic clays are found in different areas of the oceans. In the East China Sea the total amount of authigenic clays present must constitute a very minor fraction of the bottom sediments. Thus, the formation of these minerals has a relatively small impact upon dissolved Si distributions. Clay mineral reconstitution in nearshore regions may provide a mechanism for buffering sediments and overlying waters with respect to pH, as the composition of minerals formed should be a direct function of the H⁺ activity in the surrounding environment.     

Lithology, Biostratigraphy, and Magneto stratigraphy of Gas Hydrate-Bearing Sediments in the Eastern Nankai Trough

Abstract: Stratigraphic controls on the formation and distribution of gas hydrates were examined for sediments from a BH-1 well drilled in the landward slope of the Nankai Trough, approximately 60 km off Omaezaki, Japan. Three lithologic units were recognized in the 250 m-thick sequence of sediments: Unit 1 (0–70 mbsf) consists of calcareous silt and clay with thin volcanic ash layers, Unit 2 (70–150 mbsf) consists of calcareous silt and clay with volcanic ash and thin sand layers, and Unit 3 (150–250 mbsf) consists of weakly consolidated calcareous silt and clay with thick and frequent sand layers. Soupy structures and gas bubbles in the sediments indicate the presence of two hydrate zones between 40 and 130 mbsf and below 195 mbsf. Nannofossil biostratigraphy and magnetostratigraphy indicate that the sequence recovered at the BH-1 well is mostly continuous and represents sediments deposited from 0 to 1.5 Ma. Calculation of the sedimentation rate reveals a condensed section between 65 and 90 mbsf. The inferred distribution of gas hydrates in the BH-1 well appears to be strongly controlled by the stratigraphy and lithology of the sediments. Thick, gently inclined sand layers in Unit 3 provide a conduit for the migration of gases from deeper regions, and are considered responsible for the formation of the hydrate zone below 195 mbsf. At shallower levels, thin, gently inclined sand layers are also considered to allow for the migration of gases, leading to the formation of the upper hydrate zone between 40 and 130 mbsf. The overlying sub-horizontal silt and clay of the condensed section, truncating the underlying gently inclined sand and silt/clay layers, may provide an effective trap for gases supplied through the sand layers, further contributing to hydrate formation in the upper hydrate zone.     

Natural gas at thermodynamic equilibrium Implications for the origin of natural gas

It is broadly accepted that so-called 'thermal' gas is the product of thermal cracking, 'primary' thermal gas from kerogen cracking, and 'secondary' thermal gas from oil cracking. Since thermal cracking of hydrocarbons does not generate products at equilibrium and thermal stress should not bring them to equilibrium over geologic time, we would not expect methane, ethane, and propane to be at equilibrium in subsurface deposits. Here we report compelling evidence of natural gas at thermodynamic equilibrium. Molecular compositions are constrained to equilibrium,

最新国际天然气水合物研究现状与资源潜力评估(上)

地层骨架孔隙中水合物的高质量形成是开展水合物实验研究的前提和物质基础,可为我国深水油气及水合物资源开发提供理论指导。依据南海GMGS2-07井水合物层地质条件,利用TOUGH+HYDRATE数值模拟软件和自主研制的水合物反应生成装置开展数值模拟和实验研究,在验证数值模拟方法准确性和可靠性的基础上,通过控制变量法分别开展不同地层导热系数和含水饱和度条件下水合物生成质量的影响研究。结果表明：(1) 数值模拟与室内实验过程中,水合物形成时温度、压力与三相物质变化趋势一致且特征值十分接近,验证了数值模拟方法的准确性和可靠性。(2) 导热系数越大,水合物生成越快,最终形成的水合物饱和度越大,分布也更加均匀。但导热系数与最终形成水合物的饱和度的正负相关性,存在临界边界。本次所选用的反应釜尺寸,临界边界距上、右边界距离为1.8 cm,临界边界内导热系数与水合物饱和度呈正相关性,临界边界外呈负相关性。临界边界随着反应釜尺寸的增大而增大,但临界边界位置不受地层渗透率的影响。(3) 随地层含水饱和度增加,最终形成的水合物饱和度先增大后减小,峰值处含水饱和度小于初始压力条件下的理论气水比。当初始压力为7.8 MPa,含水饱和度约22.23%时,所形成的水合物饱和度最大且分布最不均匀。由此可知,选用高导热系数材料制备地层骨架、使初始含水饱和度低于气水理论比以及调整初始温压条件使之偏向相平衡曲线左方有利于形成分布均匀的高饱和水合物。研究认为深水油气含水合物固井和水合物资源钻采提供依据,为水合物商业化开采提供技术储备。

     

The Geochemical Context of Gas Hydrate in the Eastern Nankai Trough

Abstract. Geochemical studies for gas hydrate, gas and organic matter collected from gas hydrate research wells drilled at the landward side of the eastern Nankai Trough, offshore Tokai, Japan, are reported. Organic matter in the 2355 m marine sediments drilled to Eocene is mainly composed of Type III kerogen with both marine and terrigenous organic input. The gas hydrate-bearing shallow sediments are immature for hydrocarbon generation, whereas the sediments below 2100 mbsf are thermally mature. The origins of gases change from microbial to thermogenic at around 1500 mbsf.
Carbon isotope compositions of CH₄ and CO₂, and hydrocarbon compositions consistently suggest that the CH₄ in the gas hydrate-bearing sediments is generated by microbial reduction of CO₂. The δ¹³C depth-profiles of CH₄ and CO₂ suggest that the microbial methanogenesis is less active in the Nankai Trough sediments compared with other gas hydrate-bearing sediments where solid gas hydrate samples of microbial origin were recovered. Since in situ generative-potential of microbial methane in the Nankai Trough sediments is interpreted to be low due to the low total organic carbon content (0.5 % on the average) in the gas hydrate-bearing shallow sediments, upward migration of microbial methane and selective accumulation into permeable sands should be necessary for the high concentration of gas hydrate in discrete sand layers.     

Chemical composition of pore waters of bottom sediments in different Baikal basins

Results of study of pore waters of bottom sediments from different Baikal basins are presented. The most typical ion distribution patterns reflecting the Baikal sediment diagenesis are given. We have established that in areas with regular sedimentation, in the absence of faults and inflows, the sediment pore waters of three lake basins inherit the chemical composition of the Baikal water, which is stable in time and space. Changes in pore water composition mark general natural anomalies, such as the presence of active faults, tectonic movements, and inflows along permeable zones. In areas with the subsurface occurrence of gas hydrates, thorough long-term research has revealed an anomalous composition of pore waters. It has been established that the anomalies are caused by a discharge of deep-level mud-volcanic fluids. The ejected mud-volcanic waters differ from each other in mineralization, ion composition, and sources, which determines the difference in hydrate formation and the composition of gas hydrates.