天然气水合物释放甲烷对晚第四纪气候影响的古环境记录

天然气水合物作为全球碳循环中最大的碳储库,在全球变暖或海平面变化导致压力减小的情况下将分解释放大量甲烷进入水体和大气,对气候和环境造成巨大的影响。自从1995年Dickens等提出形成晚古新世温度峰值事件(LPTM)的主要原因是海底天然气水合物大规模分解释放甲烷这一假说以来,地质历史时期天然气水合物演化的研究蓬勃发展。而晚第四纪以来经历了一系列气候变化过程,在加利福尼亚的圣巴巴拉盆地、瓜伊马斯盆地、俄罗斯的贝加尔湖、格陵兰海、秘鲁、东格陵兰陆架、巴布亚新几内亚以及南海等地都记录了天然气水合物分解释放而形成的碳同位素负偏的古环境信息。主要针对这些古环境记录进行整理总结,为进一步研究天然气水合物的动态演化提供基础。     

南海东北部甲烷成因碳酸盐岩的矿物学及同位素组成(英文)

取自南海北部的3块自生碳酸盐岩主要为圆环状、结核状和结壳状。X射线衍射分析显示,这3件碳酸盐岩主要由黏土矿物、陆源碎屑(石英、长石)和碳酸盐矿物(高镁方解石和铁白云石)组成;碳氧同位素分析表明,结核状和结壳状碳酸盐岩具有极负的δ13C(分别为-32.83‰和-38.01‰PDB)和正的δ18O(分别为+2.19‰和+2.96‰PDB),不同于正常沉积的海相碳酸盐岩,甲烷厌氧氧化过程控制了这些碳酸盐岩的形成。碳酸盐岩为甲烷成因,记录了南海东北部海底富含甲烷的冷泉活动历史。     

珠江口及其邻近海域沉积物甲烷-硫酸根界面分布深度及影响因素

利用化学和稳定同位素化学等方法分析研究区沉积物间隙水甲烷和硫酸根、pH和∑CO2以及δ^13C—CH4和δ^13C—ECO2的垂直剖面分布。结果显示,间隙水硫酸根浓度呈线性梯度减小,至沉积物甲烷-硫酸盐界面（sulfate-methane interface,SMI）附近,硫酸盐几乎全部消耗而甲烷浓度急剧增大;与此同时,间隙水pH和∑CO2在该深度位置明显升高。间隙水地球化学特征揭示了沉积物发生了AOM作用。在AOM过程中,由于^12CH4氧化速率较^13CH4快,故引起沉积物间隙水剩余甲烷的碳同位素偏重,而δ^13C—ZCO2值变为极负,珠江口QA11—2、QA12-9、QA12—14和GS-1四个站位SMI对应深度分别为12cm、38cm、50cm和204cm,而南海BD-7站位由间隙水硫酸根剖面变化推算约为600cm。从珠江河口到南海沉积物,由于受陆源输入的减少,表层沉积物有机质含量呈降低趋势。有机质输入量及其活性的高低是制约了沉积物SMI分布深浅的关键因素,这是由于高含量的活性有机质一方面可加速间隙水硫酸根通过有机质再矿化分解作用途径消耗;另一方面可引起向上扩散进入AOM反应带的甲烷通量增大,使得通过AOM作用的硫酸根消耗通量相应增大,其结果造成沉积物SMI的上移。根据沉积物C／N比值以及^13C剖面变化,推断AOM作用的可能发生机制是由于在沉积物表层再矿化作用过程中,因一部分活性有机质被大量消耗,导致进入沉积物硫酸根还原带底部的活性有机质数量相应减少,从而引起部分硫酸根转为与甲烷发生反应,并在微生物的作用下完成AOM过程。     

Variability of the bottom-simulating reflector (BSR) and its association with tectonic structures in the Chilean margin between Arauco Gulf (37°S) and Valdivia (40°S)

Multichannel seismic reflection data recorded between Arauco Gulf (37°S) and Valdivia (40°S), on the Chilean continental margin, were processed and modeled to obtain seismic images and sub-surface models, in order to characterize the variability of the bottom-simulating reflector (BSR), which is a geophysical marker for the presence of gas hydrates. The BSR is discontinuous and interrupted by submarine valleys, canyons, as well as by faults or fractures. The BSR occurrence is more common south of Mocha Island due to moderate slopes and greater organic matter contribution by rivers in that area. Tectonic uplift and structural instability change the stability gas hydrate zone and consequently the BSR position, creating in some cases missing or double BSRs. Our modeling supports the presence of gas hydrate above the BSR and free gas below it. Higher BSR amplitudes support higher hydrate or free gas concentrations. In the study area, gas hydrate concentration is low (an average of 3.5%) suggesting disseminated gas hydrate distribution within the sediments. Also higher BSR amplitudes are associated with thrust faults in the accretionary prism, which serve as conduits for gas flow from deeper levels. This extra gas supply produces a wider thickness of gas hydrates or free gas.     

Geological controls on BSR occurrences in the incipient arc-continent collision zone off southwest Taiwan

Bottom simulating reflectors (BSRs) observed on seismic sections are often considered as indicators for the existence of free gas, delineating the base of the gas hydrate stability zone. Abundant BSRs seen on seismic sections acquired off the SW coast of Taiwan indicate the likely and prevalent existence of gas hydrates in the study area. This study aims to characterize the occurrence of BSRs off SW Taiwan and to understand their relationship to topography, tectonic activity, and possible migration paths of gas-bearing fluids in this area.     

Gas-hydrate promotion by smectite–bioproduct interactions

Gas hydrates accumulate on the Gulf of Mexico seafloor around hydrocarbon seeps in waters sufficiently deep to provide adequate pressure/temperature combinations. High microbial activities occur around the hydrate accumulations. To understand apparent catalytic effects of bioproducts on hydrate formation, the mechanism of sII hydrate nucleation in unconsolidated porous media was investigated in our laboratory. Because smectite clays interacting with biopolymers had been shown to promote laboratory hydrates by decreasing induction times, increasing formation rates and altering morphology, these materials commonly found in near-surface sediments were selected for study as possible nucleating agents. Dynamic light scattering (DLS) with a helium–neon laser was used to measure particle diameters down to about 2 nm. Scanning electron microscopy (SEM) was utilized to verify particle sizes and to give additional information on biopolymer–clay associations. This paper presents evidence that nanometer-sized particles of mineral–bioproduct associations of about 80 nm–450 nm diameter may act as nucleation sites for hydrate crystal initiations in sediments and then remain dispersed throughout the accumulated hydrate mass. Emulsan biopolymer was shown by SEM to apparently unfold and associate with the smectite (nontronite) in a backbone arrangement and to give multiple hydrate nucleation sites along a linear network. SEM and DLS measurements were in agreement on particle sizes and shapes. X-ray diffraction suggested that biopolymer intercalates the smectite interlayer, probably driven by clay associations with biopolymer hydrophilic groups. It is hypothesized that hydrocarbon gases attach to biopolymer hydrophobic fatty-acid branches protruding from clay interlayers and subsequently facilitate hydrate structure formation by interacting with nearby water associated with the hydrophilic segments of the biopolymer.     

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。     

硫酸盐-甲烷界面与甲烷通量及下伏水合物赋存的关系

硫酸盐-甲烷界面在富甲烷和含天然气水合物的海洋沉积区已经成为一个重要的生物地球化学识别边界.在硫酸盐-甲烷界面之上,沉积物中的硫酸盐因参与分解有机质和甲烷厌氧氧化反应而被消耗,而界面之下沉积物中的甲烷则不断生成,含量逐渐增加.根据该界面附近硫酸盐浓度和甲烷浓度的变化特征,可以判断该区甲烷流体通量的大小,从而指示下伏天然气水合物的可能赋存状况.南海北部陆坡的柱状沉积物孔隙水数据的分析显示,其硫酸盐-甲烷界面埋深比较浅,表明该海域的甲烷通量较高.这种高甲烷通量很可能是由下伏的天然气水合物所引起的,并暗示着该区下伏海底可能有天然气水合物沉积层赋存.     

Seismic imaging of a fractured gas hydrate system in the Krishna–Godavari Basin offshore India

Gas hydrate was discovered in the Krishna–Godavari (KG) Basin during the India National Gas Hydrate Program (NGHP) Expedition 1 at Site NGHP-01-10 within a fractured clay-dominated sedimentary system. Logging-while-drilling (LWD), coring, and wire-line logging confirmed gas hydrate dominantly in fractures at four borehole sites spanning a 500 m transect. Three-dimensional (3D) seismic data were subsequently used to image the fractured system and explain the occurrence of gas hydrate associated with the fractures. A system of two fault-sets was identified, part of a typical passive margin tectonic setting. The LWD-derived fracture network at Hole NGHP-01-10A is to some extent seen in the seismic data and was mapped using seismic coherency attributes. The fractured system around Site NGHP-01-10 extends over a triangular-shaped area of ∼2.5 km² defined using seismic attributes of the seafloor reflection, as well as “seismic sweetness” at the base of the gas hydrate occurrence zone. The triangular shaped area is also showing a polygonal (nearly hexagonal) fault pattern, distinct from other more rectangular fault patterns observed in the study area. The occurrence of gas hydrate at Site NGHP-01-10 is the result of a specific combination of tectonic fault orientations and the abundance of free gas migration from a deeper gas source. The triangular-shaped area of enriched gas hydrate occurrence is bound by two faults acting as migration conduits. Additionally, the fault-associated sediment deformation provides a possible migration pathway for the free gas from the deeper gas source into the gas hydrate stability zone. It is proposed that there are additional locations in the KG Basin with possible gas hydrate accumulation of similar tectonic conditions, and one such location was identified from the 3D seismic data ˜6 km NW of Site NGHP-01-10.     

Methane sources,sinks and fluxes in a temperate tidal Lagoon: The Arcachon lagoon (SW France)

The Arcachon lagoon is a 156 km² temperate mesotidal lagoon dominated by tidal flats (66% of the surface area). The methane (CH₄) sources, sinks and fluxes were estimated from water and pore water concentrations, from chamber flux measurements at the sediment–air (low tide), sediment–water and water–air (high tide) interfaces, and from potential oxidation and production rate measurements in sediments. CH₄ concentrations in waters were maximal (500–1000 nmol l⁻¹) in river waters and in tidal creeks at low tide, and minimal in the lagoon at high tide (<50 nmol l⁻¹). The major CH₄ sources are continental waters and the tidal pumping of sediment pore waters at low tide. Methanogenesis occurred in the tidal flat sediments, in which pore water concentrations were relatively high (2.5–8.0 μmol l⁻¹). Nevertheless, the sediment was a minor CH₄ source for the water column and the atmosphere because of a high degree of anaerobic and aerobic CH₄ oxidation in sediments. Atmospheric CH₄ fluxes at high and low tide were low compared to freshwater wetlands. Temperate tidal lagoons appear to be very minor contributor of CH₄ to global atmosphere and to open ocean.