Characteristics and accumulation model of the late Quaternary shallow biogenic gas in the modern Changjiang delta area, eastern China

The Changjiang（Yangtze）is one of the largest rivers in the world.It formed a huge incised valley at its mouth during the Last Glacial Maximum;the incised-valley fill,approximately 80–110 m thick,supplies an important foundation for the generation of shallow biogenic-gas reservoirs.Two cores and 13 cone penetration tests were used to elaborate the characteristics,formation mechanism,and distribution of the shallow biogenic-gas reservoirs in the study area.The natural gas is mainly composed of CH4（generally[95%）with a δ^13CCH4 and δ^13CCO2 of-75.8 to-67.7% and -34.5 to-6.6%,respectively,and a δDCH4 of-215 to-185%,indicating a biogenic origin by the carbon dioxide reduction pathway.Commercial biogenic gas occurs primarily in the sand bodies of fluvial-channel,floodplain,and paleo-estuary facies with a burial depth of 50–80 m.Gas sources as well as cap beds are gray to yellowish-gray mud of floodplain,paleoestuary,and offshore shallow marine facies.The organic matter in gas sources is dominated by immature type Ⅲ kerogen（gas prone）.The difference in permeability（about4–6 orders of magnitude）between cap beds and reservoirs makes the cap beds effectively prevent the upward escape of gas in the reservoirs.This formation mechanism is consistent with that for the shallow biogenic gas in the late Quaternary Qiantang River incised valley to the south.Therefore,this study should provide further insight into understanding the formation and distribution of shallow biogenic gas in other similar postglacial incised-valley systems.

Simulation of the Accumulation Process of Biogenic Gas Hydrates in the Shenhu Area of Northern South China Sea

Previous work has largely discussed the relations between sediment structures and accumulation of gas hydrates in the Shenhu area of South China Sea, but has not documented why the gas hydrates occurred at the seafloor topographic highs. Many gas hydrate exploration examples abroad also indicate that the saturation of gas hydrates was higher at seafloor topographic highs. This work aims to understand why gas hydrates accumulated at topographic highs and why their saturation is higher.

Ultrasound contrast agents from microbubbles to biogenic gas vesicles

Microbubbles have been the earliest and most widely used ultrasound contrast agents by virtue of their unique features:such as non-toxicity,intravenous inject-ability,ability to cross the pulmonary capillary bed,and significant enhancement of echo signals for the duration of the examination,resulting in essential preclinical and clinical applications.The use of microbubbles functional-ized with targeting ligands to bind to specific targets in the bloodstream has further enabled ultrasound molecular imaging.Nevertheless,it is very challenging to utilize targeted microbubbles for molecular imaging of extra-vascular targets due to their size.A series of acoustic nanomaterials have been developed for breaking free from this constraint.Especially,biogenic gas vesicles,gas-filled protein nanostructures from microorganisms,were engineered as thefirst biomolecular ultrasound contrast agents,opening the door for more direct visual-ization of cellular and molecular function by ultrasound imaging.The ordered protein shell structure and unique gasfilling mechanism of biogenic gas vesicles endow them with excellent stability and attractive acoustic responses.What’s more,their genetic encodability enables them to act as acoustic reporter genes.This article reviews the upgrading progresses of ultrasound contrast agents from microbubbles to biogenic gas vesicles,and the opportu-nities and challenges for the commercial and clinical translation of the nascentfield of biomolecular ultrasound.

New Approaches and Markers for Identifying Secondary Biogenic Coalbed Gas

According to the adsorption-desorption characteristics of coalbed gas and analysis of various experimental data, this paper proposes that the generation of secondary biogenic gas （SBG） and its mixing of with the residual thermogenic gas at an early stage inevitably lead to secondary changes of the thermogenic gas and various geochemical additive effects. Experimental results also show that the fractionation of the carbon isotope of methane of coal core desorption gas changes very little; the δ13C1 value of the mixed gas of biogenic and thermogenic gases is between the δ13C1 values of the two ＂original＂ gases, and the value is determined by the carbon isotopic compositions and mixing proportions of the two ＂original＂ methanes. Therefore this paper proposes that the study on the secondary changes of the thermogenic gas and various additive effects is a new effective way to study and identify SBG. Herein, a systematic example of research on the coalbed gas （Huainan coalbed gas） is further conducted, revealing a series of secondary changes and additive effects, the main characteristics and markers of which are： （1） the contents of CO2 and heavy-hydrocarbons decrease significantly; （2） the content of CH4 increases and the gas becomes drier; （3） the δ13C and δD values of methane decrease significantly and tend to have biogenetic characteristics; and （4） the values of 513C2 and δ13Cc02 grow higher. These isotopic values also change with the degradation degrees by microbes and mixing proportions of the two kinds of gases in different locations. There exists a negative correlation between the △13C1 It＇S δ13Cco2 values. The δ13Cc2-c1 values obviously become higher. The distributions of the △δ^13Cco2-C1 values are within certain limits and show regularity. There exist a positive correlation between the N2 versus Ar contents, and a negative correlation between the N2 versus CH4 contents, indicating the down forward infiltration of the surface water containing air. These are important markers of the generation and existence of SBG .

Biogenic gas generation effects on anthracite molecular structure and pore structure

This study carries out a simulated experiment of biogenic gas generation and studies the effects of gas generation on the pore structure and molecular structure of anthracite by mercury intrusion porosimetry,X-ray diffraction(XRD)and Fourier transform infrared spectroscopy(FT-IR).The results show that methanogenic bacteria can produce biogenic gas from anthracite.CO_(2) and CH4 are the main components of the generated biogas.After generation,some micropores(<10 nm)and transitional pores(10–100 nm)in the coal samples transform into large pores.In the high-pressure stage(pressure>100 MPa)of the mercury intrusion test,the specific surface area decreases by 19.79%compared with that of raw coal,and the pore volume increases by 7.25%in total.Microbial action on the molecular structure causes changes in the pore reconstruction.The FT-IR data show that the side chains and hydroxyl groups of the coal molecular structure in coal are easily metabolized by methanogenic bacteria and partially oxidized to form carboxylic acids.In addition,based on the XRD data,the aromatic lamellar structure in the coal is changed by microorganisms;it decreases in lateral size(La)and stacking thickness(Lc).This study enriches the theory of biogenic coalbed gas generation and provides a pathway for enhancing the permeability of high-rank coal reservoirs.

Status of research on biogenic coalbed gas generation mechanisms

Biogenic coalbed gas,how it is generated and the geochemical characteristics of the gas are gaining global attention.The ways coalbed gas is generated,the status of research on the generation mechanism and the methods of differentiating between biogenic gasses are discussed.The generation of biogenic coalbed methane is consistent with anaerobic fermentation theory.Commercial biogenic coalbed gas reservoirs are mainly generated by the process of CO2 reduction.The substrates used by the microbes living in the coal include organic compounds,CO2,H2 and acetate.The production ratio and quantity of biogenic coalbed methane depend on the exposed surface area,the solubility and permeability of the coal and the microbial concentration in the coal seam.It is generally believed that biogenic coalbed gas has a value for δ13C1<-5.5%,C1/C1+>0.95.The H isotope ratio is controlled by both the environment and the generation mechanism:typically δD1<-20%.Biogenic methane formed by CO2 reduction has more δD1 than that formed by acetate fermentation.

Focused fluid flow in the Baiyun Sag, northern South China Sea: implications for the source of gas in hydrate reservoirs

The origin and migration of natural gas and the accumulation of gas hydrates within the Pearl River Mouth Basin of the northern South China Sea are poorly understood. Based on high-resolution 2D/3D seismic data, three environments of focused fluid flow： gas chimneys, mud diapirs and active faults have been identified. Widespread gas chimneys that act as important conduits for fluid flow are located below bottom simulating reflections and above basal uplifts. The occurrence and evolution of gas chimneys can be divided into a violent eruptive stage and a quiet seepage stage. For most gas chimneys, the strong eruptions are deduced to have happened during the Dongsha Movement in the latest Miocene, which are observed below Pliocene strata and few active faults develop above the top of the Miocene. The formation pressures of the Baiyun Sag currently are considered to be normal, based on these terms： 1） Borehole pressure tests with pressure coefficients of 1.043-l.047; 2） The distribution of gas chimneys is limited to strata older than the Pliocene; 3） Disseminated methane hydrates, rather than fractured hydrates, are found in the hydrate samples; 4） The gas hydrate is mainly charged with biogenic gas rather than thermogenic gas based on the chemical tests from gas hydrates cores. However, periods of quiet focused fluid flow also enable the establishment of good conduits for the migration of abundant biogenic gas and lesser volumes ofthermogenic gas. A geological model goveming fluid flow has been proposed to interpret the release of overpressure, the migration of fluids and the formation of gas hydrates, in an integrated manner. This model suggests that gas chimneys positioned above basal uplifts were caused by the Dongsha Movement at about 5.5 Ma. Biogenic gas occupies the strata above the base of the middle Miocene and migrates slowly into the gas chimney columns. Some of the biogenic gas and small volumes ofthermogenic gas eventually contribute to the formation of the gas hydrates.

Coalbed methane genesis, occurrence and accumulation in China

Coalbed methane （CBM） is an important type of unconventional gas. Commercial development of CBM in America has been very successful since the 1980s. The CBM industry in Australia and Canada has developed rapidly during the last decade. Commercial development of CBM in China started in the 1990s, and has made great progress. The geological theory of CBM in China has achieved great advancement in genesis, occurrence and accumulation. On the aspect of CBM genesis, five CBM genetic types （primary biogenic gas, secondary biogenic gas, thermal degradation gas, pyrolysis gas and mixed gas） are identified by studying the geochemical characteristics of CBM, and a tracing indicator system is established. The discovery of secondary biogenic gas in medium-high rank coal reservoirs has widened the potential of CBM resources. On the aspect of CBM occurrence, the gas adsorption regulation under combined action of temperature and pressure is revealed by conducting adsorption experiments of different coal ranks under varying temperature and pressure conditions. Besides, by applying the adsorption potential theory in CBM research, the adsorption model under combined action of temperature and pressure is established. The new model can predict CBM resources accurately, and overcome the limitation of the traditional Langmuir model which uses just a single factor to describe the adsorption characteristics of deep buried coal. On the aspect of CBM accumulation, it is proposed that there are three evolutionary stages during CBM accumulation, including gas generation and adsorption, unsaturated gas adsorption, gas desorption-diffusion and preservation. Controlled by tectonic evolution, hydrodynamics and sealing conditions, CBM tends to be regionally enriched in synclines. Advances in geological theory of CBM in China can not only improve understanding of natural gas, but also provide new ideas for further exploration of CBM.

Internal Structure of the Incised Valley Fill in the Hangzhou Bay, Eastern China and Its Geological Implications

This paper presents the sedimentary facies and formation of the Qiantangjiang and Taihu incised valleys, and the characteristics of shallow gas reservoir distribution, based on a large number of data of drilling, static sounding and chemical analysis obtained from the present Hangzhou Bay coastal plain. The incised valleys were formed during the last glacial maximum and were subsequently filled with fluvial facies during the post-glacial period. All commercial gases are stored in the flood plain sand lenses of the incised valleys.