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.     

南海北部陆坡珠江口盆地东南海域GMGS2-09井孔隙水地球化学特征及其对天然气水合物的指示意义

沉积物孔隙水地球化学是天然气水合物勘探与研究的重要手段。为了探究珠江口盆地东南海域GMGS2-09钻孔的沉积物孔隙水地球化学特征及其对埋藏的天然气水合物的指示意义,我们在前人的研究和认知基础上,通过测试该钻孔沉积物孔隙水的氯离子含量、氢氧同位素和阳离子组成来识别天然气水合物的赋存层位。结果表明GMGS2-09钻孔在9~17、47以及100m处存在氯离子浓度的负异常耦合氧同位素的正异常,指示相应的天然气水合物赋存,其中9~17m层位指示结果与实际取样情况完全一致。此外,采用基于水合物晶格的排盐机理推导的经验公式计算显示水合物饱和度在浅表层(17m)最高约为50%,中间以及底层约为20%。     

Contribution of thermogenic organic matter to the formation of biogenic gas hydrate: Evidence from geochemical and microbial characteristics of hydrate-containing sediments in the Taixinan Basin,South China Sea

High-saturation (40–100%), microbial gas hydrates have been acquired by expedition GMGS2 from the Taixinan Basin. In this study, geochemical and microbial features of hydrate-containing sediments from the drilling cores (GMGS2-09 and GMGS2-16) were characterized to explore their relationships with gas hydrate formation. Results showed that the average TOC content of GMGS2-09 and GMGS2-16 were 0.45% and 0.63%, respectively. They could meet the threshold for in situ gas hydrate formation, but were not available for the formation of high-saturation gas hydrates. The dominant members of Bacteria at the class taxonomic level were Alphaproteobacteria, Bacilli, Bacteroidia, Epsilonproteobacteria and Gammaproteobacteria, and those in Archaea were Marine_Benthic_Group_B (MBGB), Miscellaneous_Crenarchaeotic_Group (MCG), Group C3, Methanomicrobia and Methanobacteria. Indicators of microbes associated with thermogenic organic matter were measured. These include: (1) most of the dominant microbes had been found dominant in other gas hydrates bearing sediments, mud volcanos as well as oil/coal deposits; (2) hydrogenotrophic methanogens and an oilfield-origin thermophilic, methylotrophic methanogen were found dominant the methanogen community; (3) hydrocarbon-assimilating bacteria and other hyperthermophiles were frequently detected. Therefore, thermogenic signatures were inferred existed in the sediments. This deduction is consistent with the interpretation from the seismic reflection profiles. Owing to the inconsistency between low TOC content and gas hydrates with high saturation, secondary microbial methane generated from the bioconversion of thermogenic organic matters (oil or coal) was speculated to serve as enhanced gas flux for the formation of high-saturation gas hydrates. A preliminary formation model of high-saturation biogenic gas hydrates was proposed, in which diagenesis processes, tectonic movements and microbial activities were all emphasized regarding to their contribution to gas hydrates formation. In short, this research helps explain how microbial act and what kind of organic matter they use in forming biogenic gas hydrates with high saturations.