Sources and sinks of atmospheric methane

In 1972 average mixing ratio of methane in the troposphere was 1.41 ppm and 1.3 ppmv for the northern and southern hemisphere, respectively, which corresponds to a total amount of 4×10¹⁵ g of CH₄ present in the atmosphere. Most is of recent biologic origin.¹⁴C analyses show that no more than 20 percent is released by fossil sources. The various ecosystems producing CH₄ are discussed and the total annual production is estimated to lie between 5.5×10¹⁴ g/yr and 11×10¹⁴ g/yr. The corresponding turnover times for atmospheric CH₄ range from 4 to 7 yrs. The destruction of CH₄ takes place mainly in the troposphere, most probably through the reaction of CH₄ + OH CH₃ + H₂O. About 10 percent of the CH₄ is destroyed in the stratosphere. The CH₄ cycle contributes on the order of 1 percent to the atmospheric carbon cycle.     

Mitigating Agricultural Emissions of Methane

Agricultural crop and animal production systems are important sources and sinks for atmospheric methane (CH4). The major CH4 sources from this sector are ruminant animals, flooded rice fields, animal waste and biomass burning which total about one third of all global emissions. This paper discusses the factors that influence CH4 production and emission from these sources and the aerobic soil sink for atmospheric CH4 and assesses the magnitude of each source. Potential methods of mitigating CH4 emissions from the major sources could lead to improved crop and animal productivity. The global impact of using the mitigation options suggested could potentially decrease agricultural CH4 emissions by about 30%.     

Hydrogeochemical models locating sulfate-methane transition zone in marine sediments overlying black shales: A new tool to locate biogenic methane?

Precise hydrogeochemical modeling of early diagenesis is a key in the reconstruction of sedimentary basin models. This determines the mineralogical evolution of the sediment and consequently the porosity of the rock. During early diagenesis also part of the initial organic matter is converted into biogenic gas: CH₄ CO₂, and H₂S. These processes are part of complex reaction chains during sedimentation, and biogeochemical reactions leave different signals that can be observed today. In this work, we reproduce the early diagenetic processes as integrated signals over geological times in sediments of the Demerara Rise by applying chemical thermodynamics using the PHREEQC (version 2) computer code. The investigated sediments are characterized by the presence of black shales in 410–490 mbsf and by a diagenetic barite layer above in 300–350 mbsf at depth of sulfate-methane transition (SMT). We determine the parameters that influence the location of diagenetic barite peaks in sediments overlying black shales by means of a novel modeling approach. Crucial parameters are the amount of bacterial organic matter mineralization, sedimentation rates and bottom water sulfate concentrations. All parameters are intertwining and influence the sulfate-methane cycle. They affect the location of the SMT visualized by diagenetic barite peaks. However, our model approach opens a wide field in exploring early diagenetic reactions, processes and products (such as biogenic methane) over geological times mirrored by diagenetic minerals and pore water concentration profiles that can be detected in present-day sediments.     

Paragenesis of fluids under evaporates in the Volga-Ural Basin

To unravel the mystery of the relationship between evaporates, Ca–Cl brines and accumulations of oil and N₂ in the basins of ancient cratons, their N₂, CH₄ and He concentration ratios, as well as the isotopic composition (δ¹⁵N, δ¹³C and ³He/⁴He) were compared within the Volga-Ural basin. The study allowed subsalt fluids from Volga-Ural Basin to divide into two genetic groups. The first one is found within the basin's platform area. It includes Ca–Cl brines, high-viscosity heavy oil, bitumen and N₂, which has concentrations higher than that of CH₄ and positive values of δ¹⁵N. The second one is tied to the edge of the platform, the Ural Foredeep and Peri-Caspian Depression. In this group, only the oil and gas reservoirs, which have more CH₄ than N₂, and possibly negative values of δ¹⁵N, were discovered. Interaction of gas components in compared fluids indicates great role of degassing in the formation of their composition. It is suggested that the fluids of the first group (N₂ > CH₄) is what remains, and the second group (N₂ < CH₄) is what is disappears from the rocks during their metamorphism and degassing.     

Megaplume bubble process visualization by 3D multibeam sonar mapping

MultiBeam echosounder data were collected during a surface-ship survey of the 22/4b well site in the North Sea in September 2011 using a Teledyne-Reson 7125. Modern multibeam echosounders are instrumental in providing detection and accurate localization of weak to strong bubble plumes. Two survey profiles effectively insonified the bubble plumes rising from the main crater at the well site, providing snapshot data of bubble plume processes. Additionally, three profiles insonified bubble plumes rising from, in, and to the south of a secondary crater, 1.2 km southeast of the main crater. Data processing included a simple algorithm that muted mislocated echoes from incomplete sidelobe suppression. The data processing produced a Cartesian volume of echo intensity from the water column and seabed.Plume geometry was analyzed to investigate a number of important large-scale plume processes, including plume bubble detrainment due to currents and stratification, downwelling flows, sea surface interaction, plume heterogeneity, and other fluid transport processes. The data showed strong upwelling flows, with bubble vertical motions generally much faster than currents. One important finding was that megaplumes create intrusions above the general thermocline, in part because their extensive upwelling flow lifts the thermocline locally. As a result, the intrusion layer deposits dissolved gases in the upper wave-mixed layer of the water column where it is not isolated from the atmosphere, unlike dissolved gases in the lower water column.The analysis shows that high fidelity multibeam echosounder data can provide a wealth of remote sensing information on bubble plume characteristics and processes, with important applications, including blowout monitoring and response, better understanding of megaplumes such as used in lake destratification, and improved characterization of natural seep emission processes.     

Continuous inline mapping of a dissolved methane plume at a blowout site in the Central North Sea UK using a membrane inlet mass spectrometer – Water column stratification impedes immediate methane release into the atmosphere

The dissolved methane (CH₄) plume rising from the crater of the blowout well 22/4b in the Central North Sea was mapped during stratified water column conditions. Geochemical surveys were conducted close to the seafloor at 80.3 m water depth, below the thermocline (61.1 m), and in the mixed surface layer (13.2 m) using membrane inlet mass spectrometry (MIMS) in combination with a towed CTD. Seawater was continuously transferred from the respective depth levels of the CTD to the MIMS by using an inline submersible pump. Close to the seafloor a well-defined CH₄ plume extended from the bubble release site ∼460 m towards the southwest. Along this distance CH₄ concentrations decreased from a maximum of 7872 nmol l⁻¹ to less than 250 nmol l⁻¹. Below the thermocline the well-defined CH₄ plume shape encountered at the seafloor was distorted and filaments were observed that extended towards the west and southwest in relation to current direction. Where the core of the bubble plume intersected this depth layer, footprints of high CH₄ concentrations of up to 17,900 nmol l⁻¹ were observed. In the mixed surface layer the CH₄ distribution with a maximum of up to 3654 nmol l⁻¹ was confined to a small patch of ∼60 m in diameter. The determination of the water column CH₄ inventories revealed that CH₄ transfer across the thermocline was strongly impeded as only ∼3% of the total water column inventory was located in the mixed surface layer. Best estimate of the CH₄ seabed release from the blowout was 1751 tons yr⁻¹. The fate of the trapped CH₄ (∼97%) that does not immediately reach the atmosphere remains speculative. In wintertime, when the water column becomes well mixed as well as during storm events newly released CH₄ and the trapped CH₄ pool can be transported rapidly to the sea surface and emitted into the atmosphere.     

Combined experimental and theoretical studies on methane photolysis at 121.6 and 248 nm—implications on a program of laboratory simulations of Titan’s atmosphere

Methane is, together with N₂, the main precursor of Titan’s atmospheric chemistry. In our laboratory, we are currently developing a program of laboratory simulations of Titan’s atmosphere, where methane is intended to be dissociated by multiphotonic photolysis at 248 nm. A preliminary study has shown that multiphotonic absorption of methane at 248 nm is efficient and leads to the production of hydrocarbons such as C₂H₂ (Romanzin et al., 2008). Yet, at this wavelength, little is known about the branching ratios of the hydrocarbon radicals (CH₃, CH₂ and CH) and their following photochemistry. This paper thus aims at investigating methane photochemistry at 248 nm by comparing the chemical evolution observed after irradiation of CH₄ at 248 and at 121.6 nm (Ly-α). It is indeed important to see if the chemistry is driven the same way at both wavelengths in particular because, on Titan, methane photolysis mainly involves Ly-α photons. An approach combining experiments and theoretical analysis by means of a specifically adapted 0-D model has thus been developed and is presented in this paper. The results obtained clearly indicate that the chemistry is different depending on the wavelength. They also suggest that at 248 nm, methane dissociation is in competition with ionisation, which could occur through a three-photon absorption process. As a consequence, 248 nm photolysis appears to be unsuitable to study methane neutral photochemistry alone. The implications of this result on our laboratory simulation program and new experimental developments are discussed. Additional information on methane photochemistry at 121.6 nm are also obtained.     

南海神狐海域水合物三相混合层测井评价方法研究

天然气水合物降压试采过程中,水合物、游离气和水的三相混合层中的游离气首先被采出,从而提高降压效率,促进水合物分解;因此利用岩心刻度测井的方法开展南海神狐海域水合物三相混合层测井评价方法研究,对水合物矿体储量计算以及产业化开采具有重要意义.三相混合层与水合物层相比,其密度和中子孔隙度值均减小,纵波速度明显下降;与气层相比...     

Excess of bottom-released methane in an Arctic shelf sea polynya in winter

Latent heat polynyas are regions generating strong ice formation, convection and extensive water mass formation. Here we report on the effects of these processes on resuspension of sediments and subsequent methane release from the seafloor and on the resulting excess methane concentration in surface water on a polar shelf during winter. The study is based on measurements of concentration and δ¹³C values of methane, water temperature, salinity, light transmission and sea ice data collected in March 2003 in Storfjorden, southern Svalbard. In winter, strong and persistent northeasterly winds create polynyas in eastern Storfjorden and cause ice formation. The resulting brine-enriched water cascades from the Storfjordbanken into the central depression thereby enhancing the turbulence near the seafloor. A distinct benthic nepheloid layer was observed reflecting the resuspension of sediments by the cascading dense bottom water. High concentrations of ¹³C-depleted methane suggest submarine discharge of methane with the resuspended sediments. As the source of the submarine methane, we propose recent bacterial methanogenesis near the sediment surface because of extremely high accumulation rates of organic carbon in Storfjorden. Convective mixing transports newly released methane from the bottom to the sea surface. This eventually results in an excess concentration in surface water with respect to the atmospheric equilibrium, and a sea-air flux of methane during periods of open water. When a new ice cover is formed, methane becomes trapped in the water column and subsequently oxidized. Thus, the residual methane is strongly enriched in ¹³C in relation to the δ¹³_CCH4${\delta }^{13}{\mathrm{C}}_{{\mathrm{CH}}_4}$ signature of atmospheric methane. Our results show that latent heat polynyas may induce a direct pathway for biogases like methane from sediments to the atmosphere through coupling of biogeochemical and oceanographic processes. Extrapolating these processes to all Arctic ocean polynyas, we estimate a transfer of CH₄ between 0.005 and 0.02 Tg yr⁻¹. This is not a large contribution but the fluxes from the polynyas are 20–200 times larger than the ocean average and the methane evasion process in polynyas is certainly one that can be altered under climate change.     

天然气水合物开发安全检测技术应用研究

中国近年来先后在南海北部和祁连山南缘青海省天峻县永久冻土带中发现天然气水合物,这是一种新能源,它将对中国能源结构的调整和能源紧张的缓解起到非常重要的作用。但是,天然气水合物开采安全是个大问题,已经引起了国际上专家们的极大关注。俄罗斯南方国立技术大学地球物理、探矿工程和石油钻采教研室开发出来的天然气水合物开发安全检测技术和方法,可以准确确定出射孔部位的位置、检查射孔部位是否阻塞和如何解阻等关键技术,对天然气水合物开采安全提供了技术支撑,对此应该进行研究。