天然气水合物赋存区甲烷渗漏活动的地球化学响应特征

综述了天然气水合物赋存区甲烷渗漏活动的地球化学响应指标的研究进展,分析了应用单一指标识别甲烷渗漏活动各自所存在的问题,包括浅表层沉积物孔隙水中CH_4、SO_4~(2–)、Cl~–等离子浓度随深度的变化;浅层沉积物全岩W_(TOC)(W表示质量分数,TOC表示总有机碳)和W_(TS)(TS表示总硫)之间的相关性及比值;自生碳酸盐岩δ~(13)C和δ~(18)O;自生矿物重晶石、黄铁矿、自生石膏的δ~(34)S;有孔虫壳体和生物标志化合物的δ~(13)C等。结果表明孔隙水中的CH_4、SO4_~(2–)浓度及溶解无机碳的碳同位素组成可以用来识别目前正在发生的甲烷渗漏活动;而沉积物中的WTS、自生矿物的δ~(34)S、钡含量及其异常峰值和生物标志化合物的δ~(13)C等指标的联合使用可以更真实准确地反映地质历史时期天然气水合物赋存区的甲烷渗漏活动。因此,在实际研究过程中,可将孔隙水和沉积物两种介质的多种指标相结合。随着非传统稳定同位素(Fe、Ca、Mg等)和沉积物氧化还原敏感元素(Mo、V、U等)等研究的发展,甲烷渗漏活动地球化学响应指标的研究也将得到拓展,而多种地球化学指标的联合使用将为天然气水合物勘探及其形成分解过程识别研究提供重要的科学依据。     

深海热液区主要成分的高温高压拉曼光谱分析

模拟深海热液口环境(最高压力40 MPa,最高温度350℃),对深海热液区的主要成分CO2、CH4及其混合物的水溶液在不同压力和温度条件下的拉曼光谱进行探测和分析,结果显示:常温低压下CO2水溶液的Fermi双峰分别位于1 384.9 cm-1和1 278.3 cm-1处,CH4的水溶液拉曼峰υ1位于2 912.1 cm-1处,均比其气相的拉曼频移小;常温下CO2和CH4水溶液的拉曼特征峰随压力(≤40 MPa)的变化均不明显;在40 MPa的压力下随着温度的升高(≤350℃),CO2水溶液的Fermi双峰分别向高波数区移动了约3.4 cm-1和7.0 cm-1,而CH4水溶液的拉曼峰υ1向低波数区移动了约3.1cm-1;混合后升温过程中CO2的双峰分别向高波数区移动了约4.3 cm-1和3.8 cm-1,CH4的特征峰υ1向低波数区移动了4.5 cm-1。说明在室温到350℃范围内温度的变化对CO2和CH4水溶液拉曼频移有影响,频移量与温度线性相关,而压力在≤40 MPa范围内的改变对拉曼频移影响不明显。     

A predictive numerical model for potential mapping of the gas hydrate stability zone in the Gulf of Cadiz

This paper presents a computational model for mapping the regional 3D distribution in which seafloor gas hydrates would be stable, that is carried out in a Geographical Information System (GIS) environment. The construction of the model is comprised of three primary steps, namely: (1) the construction of surfaces for the various variables based on available 3D data (seafloor temperature, geothermal gradient and depth-pressure); (2) the calculation of the gas function equilibrium functions for the various hydrocarbon compositions reported from hydrate and sediment samples; and (3) the calculation of the thickness of the hydrate stability zone. The solution is based on a transcendental function, which is solved iteratively in a GIS environment.The model has been applied in the northernmost continental slope of the Gulf of Cadiz, an area where an abundant supply for hydrate formation, such as extensive hydrocarbon seeps, diapirs and fault structures, is combined with deep undercurrents and a complex seafloor morphology. In the Gulf of Cadiz, the model depicts the distribution of the base of the gas hydrate stability zone for both biogenic and thermogenic gas compositions, and explains the geometry and distribution of geological structures derived from gas venting in the Tasyo Field (Gulf of Cadiz) and the generation of BSR levels on the upper continental slope.     

Experimental formation of massive hydrate deposits from accumulation of CH4 gas bubbles within synthetic and natural sediments

In order for methane to be economically produced from the seafloor, prediction and detection of massive hydrate deposits will be necessary. In many cases, hydrate samples recovered from seafloor sediments appear as veins or nodules, suggesting that there are strong geologic controls on where hydrate is likely to accumulate. Experiments have been conducted examining massive hydrate accumulation from methane gas bubbles within natural and synthetic sediments in a large volume pressure vessel through temperature and pressure data, as well as visual observations. Observations of hydrate growth suggest that accumulation of gas bubbles within void spaces and at sediment interfaces likely results in the formation of massive hydrate deposits. Methane hydrate was first observed as a thin film forming at the gas/water interface of methane bubbles trapped within sediment void spaces. As bubbles accumulated, massive hydrate growth occurred. These experiments suggest that in systems containing free methane gas, bubble pathways and accumulation points likely control the location and habit of massive hydrate deposits.     

The thermal structure of the Dvurechenskii mud volcano and its implications for gas hydrate stability and eruption dynamics

The sediment temperature distribution at mud volcanoes provides insights into their activity and into the occurrence of gas hydrates. If ambient pressure and temperature conditions are close to the limits of the gas hydrate stability field, the sediment temperature distribution not only limits the occurrence of gas hydrates, but is itself influenced by heat production and consumption related to the formation and dissociation of gas hydrates. Located in the Sorokin Trough in the northern Black Sea, the Dvurechenskii mud volcano (DMV) was in the focus of detailed investigations during the M72/2 and M73/3a cruises of the German R/V Meteor and the ROV Quest 4000 m in February and March 2007. A large number of in-situ sediment temperature measurements were conducted from the ROV and with a sensor-equipped gravity corer. Gas hydrates were sampled in pressurized cores using a dynamic autoclave piston corer (DAPC). The thermal structure of the DMV suggests a regime of fluid flow at rates decreasing from the summit towards the edges of the mud volcano, accompanied by intermittent mud expulsion at the summit. Modeled gas hydrate dissociation temperatures reveal that the gas hydrates at the DMV are very close to the stability limits. Changes in heat flow due to variable seepage rates probably do not result in changes in sediment temperature but are compensated by gas hydrate dissociation and formation.     

Characterisation and preliminary quantification of the methane reservoir in a coastal sedimentary source: San Simón Bay,Ría de Vigo,NW Spain

Ría de Vigo is a river valley flooded by the sea, with a bay (San Simón Bay) at its innermost part. The accumulation of Holocene sediment in San Simón Bay has been studied by the integration of 1) large scale high resolution seismic data, and 2) detailed geochemical analysis of a gravity core. In San Simón Bay the majority of the seismic records are obscured by acoustic turbidity which represents gassy sediments, but on records from Rande Strait it is possible to distinguish two Quaternary seismic sequences; an Upper Pleistocene sequence (SQ1) and a Holocene sequence (SQ2). Only SQ2 is recognized in San Simón Bay where it is comprised of two seismic units; the upper unit represents the HST sediment, i.e. the period of highest sea level. A gravity core taken within the gassy zone at 10 m water depth provided 3.55 m of fine-grained sediments (muds) from the youngest seismic unit (4 m thick). Geochemical analysis show high values (4 to 10%) of TOC. Sediment and porewater analyses indicate a distinct sulphate–methane transition zone (SMTZ) between 60 and 80 cm where sulphate is depleted (to <1.7 mM) and methane increases (to >0.4 mM). The top of the acoustic turbidity (the gas front) at 80 cm corresponds to the lower limit of the SMTZ. The methane cannot have been derived from the underlying metamorphic and granitic rocks, but was probably derived by microbial degradation of the organic matter in the Holocene sediments. We estimate that the sediments of the Bay contain approximately 1.8 × 10⁶ m³ of organic carbon and 275 ton of methane.     

南海中部和北部上层海水中溶存甲烷浓度及海气交换通量*

根据2010年4—5月国家基金委南海多学科综合航次在南海中部和北部的调查资料,利用抽真空气相色谱法测定海水中溶存甲烷浓度,分析了该海区上层海水中溶存甲烷的浓度、饱和度及海气交换通量。南海中部和北部表层海水中溶存甲烷浓度范围为1.15—5.6nmol·L?1,平均值为2.2nmol·L?1,饱和度范围为59.7%—298.8%,59%站位的溶存甲烷处于过饱和状态。甲烷海气交换通量范围分别为?17.7—61.3μmol·m?2·d?1(根据 LM-86方程计算)和?27.9—119.6μmol·m?2·d?1(根据 W-92方程计算)。南海是大气中甲烷的来源之一,年甲烷辐射量估算值为2.7×10?2—4.0×10?2Tg·a?1。     

Seasonal Study of Methane and Nitrous Oxide in the Coastal Waters of the Southern Baltic Sea

Atmospheric and dissolved methane (CH₄) and nitrous oxide (N₂O) were measured in the unique coastal ecosystem of theBoddenwaters, including the western Oder estuary, (southern Baltic Sea) during five campaigns between 1994 and 1997. The CH₄saturations, ranging from 105–15 500%, showed great spatial and temporal variability with maximum values in September and minimum values in December. The N₂O saturations were in the range of 91–312% with a maximum in March. Enhanced concentrations of both gases were observed only in the western Oder estuary near the mouth of the Peene River. Thus, we conclude that the distributions of CH₄and N₂O in the investigatedBoddenwaters are, directly or indirectly, linked to the Peene River runoff and not to the Oder River. Our estimate of the annual CH₄emissions from theBoddenwaters to the atmosphere indicates a significant contribution (c. 17%) to the overall CH₄emissions from the Baltic Sea. In contrast, theBoddenwaters represent only a small source for atmospheric N₂O.CH₄production rates estimated from sediment slurry experiments revealed a significant spatial variability and indicated that methanogenic activity was related to acetate consumption in the surface sediment layer. Sedimentary CH₄production might depend on different amounts of accumulation of organic material.     

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.     

冷泉系统甲烷气体渗漏的声学特征及潜在环境效应

The amount of methane leaked from deep sea cold seeps is enormous and potentially affects the global warming,ocean acidification and global carbon cycle. It is of great significance to study the methane bubble movement and dissolution process in the water column and its output to the atmosphere. Methane bubbles produce strong acoustic impedance in water bodies, and bubble strings released from deep sea cold seeps are called "gas flares"which expressed as flame-like strong backscatter in the water column. We characterized the morphology and movement of methane bubbles released into the water using multibeam water column data at two cold seeps. The result shows that methane at site I reached 920 m water depth without passing through the top of the gas hydrate stability zone(GHSZ, 850 m), while methane bubbles at site II passed through the top of the GHSZ(597 m) and entered the non-GHSZ(above 550 m). By applying two methods on the multibeam data, the bubble rising velocity in the water column at sites I and II were estimated to be 9.6 cm/s and 24 cm/s, respectively. Bubble velocity is positively associated with water depth which is inferred to be resulted from decrease of bubble size during methane ascending in the water. Combined with numerical simulation, we concluded that formation of gas hydrate shells plays an important role in helping methane bubbles entering the upper water bodies, while other factors, including water depth, bubble velocity, initial kinetic energy and bubble size, also influence the bubble residence time in the water and the possibility of methane entering the atmosphere. We estimate that methane gas flux at these two sites is 0.4×10~6–87.6×10~6 mol/a which is extremely small compared to the total amount of methane in the ocean body, however, methane leakage might exert significant impact on the ocean acidification considering the widespread distributed cold seeps. In addition, although methane entering the atmosphere is not observed, further research is still needed to understand its potential impact on increasing methane concentration in the surface seawater and gas-water interface methane exchange rate, which consequently increase the greenhouse effect.