Methane hydrate dissolution rates in undersaturated seawater under controlled hydrodynamic forcing

The dissolution of in-situ generated methane hydrate in undersaturated, synthetic seawater (S = 35) was investigated in a series of laboratory-based experiments at P-/T-conditions within the hydrate stability field. A controlled flow field was generated across the smooth hydrate surface to test if, in addition to thermodynamic variables, the dissolution rate is influenced by changing hydrodynamic conditions. The dissolution rate was found to be strongly dependent on the friction velocity, showing that hydrate dissolution in undersaturated seawater is a diffusion-controlled process. The experimental data was used to obtain diffusional mass transfer coefficients k_d, which were found to correlate linearly with the friction velocity, u. The resulting k_d/u-correlation allows predicting the flux of methane from natural gas hydrate exposures at the sediment/seawater interface into the bulk water for a variety of natural P, T and flow conditions. It also is a tool for estimating the rate of hydrate regrowth at locations where natural hydrate outcrops at the seafloor persist in contact with undersaturated seawater.     

Modeling of rising methane bubbles during production leaks from the gas hydrate sites of India

Natural gas hydrates is considered as a strategic unconventional clean hydrocarbon resource in the energy sector. Understanding the behavior of the rising methane gas bubbles during production leaks from the deep marine gas hydrate reservoirs well head is essential for environmental impact studies and to design environmental monitoring systems. Numerical model for quantitatively characterizing the vertical dissolution pattern of the wellhead released methane gas bubbles is analyzed for three potential gas hydrate locations in India. Simulation results indicate that the methane bubbles with diameter of 10?mm can transport methane gas till 650, 800, and 750?m from the seabed in the Krishna–Godavari(KG), Mahanadi and Andaman basins respectively. Results brought out that potential well head damage during methane hydrate production at 1050?m water depth could release up to 28?m³ of methane gas, in which 50% of the molar mass shall get dissolved within 40?m of water column from the seafloor.     

Determination of gas bubble fractionation rates in the deep ocean by laser Raman spectroscopy

A new deep-sea laser Raman spectrometer (DORISS—Deep Ocean Raman In Situ Spectrometer) is used to observe the preferential dissolution of CO₂ into seawater from a 50%–50% CO₂–N₂ gas mixture in a set of experiments that test a proposed method of CO₂ sequestration in the deep ocean. In a first set of experiments performed at 300 m depth, an open-bottomed 1000 cm³ cube was used to contain the gas mixture; and in a second set of experiments a 2.5 cm³ funnel was used to hold a bubble of the gas mixture in front of the sampling optic. By observing the changing ratios of the CO₂ and N₂ Raman bands we were able to determine the gas flux and the mass transfer coefficient at 300 m depth and compare them to theoretical calculations for air–sea gas exchange. Although each experiment had a different configuration, comparable results were obtained. As expected, the ratio of CO₂ to N₂ drops off at an exponential rate as CO₂ is preferentially dissolved in seawater. In fitting the data with theoretical gas flux calculations, the boundary layer thickness was determined to be  42 μm for the gas cube, and  165 μm for the gas funnel reflecting different boundary layer turbulence. The mass transfer coefficients for CO₂ are k_L = 2.82 × 10^− 5 m/s for the gas cube experiment, and k_L = 7.98 × 10^− 6 m/s for the gas funnel experiment.     

深海环境中溢油输移扩散的初步数值模拟

通过对溢油在深海环境中的输移过程及行为特点的分析,初步建立基于拉格朗日积分法的深海溢油模型.该模型除了能够模拟油气混合物在真实深海环境中的共同输移与分离输移扩散过程,还考虑了石油溶解、气体溶解、天然气水合物形成与分解等行为变化对溢油运动轨迹的影响.应用该模型初步数值模拟了一次实际深海溢油试验,结果表明溢油在水下的空间分...     

Hydrochemical and atmochemical mercury dispersion zones over hydrothermal vents of the submarine Piip Volcano in the Bering Sea

Signs of mercury input and dispersion in the water mass and the atmosphere over the submarine Piip Volcano have been revealed. The mercury from hydrothermal vents has been found to release mostly as a component of hydrothermal-gas bubbles rising through the water mass to the sea’s surface. The mercury’s dispersion and the seawater’s enrichment with it is a consequence of the partial dissolution of the gas bubbles. The atmochemical dispersion zone is represented by an area of higher mercury concentration with two maximums shifted in the direction of the wind (northeastward) from the northern and southern peak of the volcano.     

A Practical bi-parameter formula of gas transfer velocity depending on wave states

The parameter that describes the kinetics of the air-sea exchange of a poorly soluble gas is the gas transfer velocity which is often parameterized as a function of wind speed. Both theoretical and experimental studies suggest that wind waves and their breaking can significantly enhance the gas exchange at the air-sea interface. A relationship between gas transfer velocity and a turbulent Reynolds number related to wind waves and their breaking is proposed based on field observations and drag coefficient formulation. The proposed relationship can be further simplified as a function of the product of wind speed and significant wave height. It is shown that this bi-parameter formula agrees quantitatively with the wind speed based parameterizations under certain wave age conditions. The new gas transfer velocity attains its maximum under fully developed wave fields, in which it is roughly dependent on the square of wind speed. This study provides a practical approach to quantitatively determine the effect of waves on the estimation of air-sea gas fluxes with routine observational data.     

Influence of processes in the ocean–atmosphere system in the North Atlantic on the intraannual variation of climatic characteristics on the territory of Ukraine

We make an attempt to study specific features of weather- and climate-forming processes developing due to the energy and mass transfer between the ocean and the atmosphere in the North Atlantic, as well as responses of the climate of Ukraine to the main climate-forming factors. These studies are based on a statistical model in the form of a system of third-order regression equations with feedback. We deduce a system of generating functions that allow us to estimate the regression coefficients. Within the developed model, we applied the factor analysis to compress the input information about the affecting factors in the region where the weather ships were located. This allowed us to reveal the tendencies of variations in the characteristics participating in the energy and mass transfer. The response of the climate in various regions of Ukraine to the processes running in the North Atlantic was determined using the cluster analysis whose algorithm was developed by the authors. We performed a number of experiments for various situations in the region of the North Atlantic that are possible due to the global warming of the climate and studied the response of climatic characteristics on the territory of Ukraine under similar processes. The adequacy of the developed model was verified on the basis of data on the real situation in February 2006. It is shown that the model satisfactorily describes the responses of climatic characteristics in regions of Ukraine to variations of the affecting factors in the North Atlantic.     

Dynamics of trace gases and aerosols in the atmosphere with consideration for heterogeneous processes

A combined mathematical model has been developed to reproduce space and time variations in the concentrations of multicomponent gas constituents and aerosols in the atmosphere on both regional and urban scales. This model contains blocks of transport of gas constituents and aerosols in the atmosphere with consideration for homogeneous binary nucleation, the kinetic processes of condensation/evaporation and coagulation, chemical processes occurring in both gas and liquid phases, and the processes of mass exchange during the gas-droplet (particle) interaction. A nonhydrostatic model of atmospheric mesoscale processes is used to calculate the fields of meteorological elements and turbulent characteristics. The generation of new-phase particles from precursor gases by the mechanism of homogeneous binary nucleation and their interaction with background aerosol are considered. The results of numerical experiments are compared with the data obtained from field observations of both space and time variations in the concentrations of gas constituents and aerosols and in the ionic content of aerosol particles over the Baikal region under the influence of emissions from powerful industrial sources.     

One-dimensional modelling of convective CO2 exchange in the Tropical Atlantic

Diurnal changes in seawater temperature affect the amount of air–sea gas exchange taking place through changes in solubility and buoyancy-driven nocturnal convection, which enhances the gas transfer velocity. We use a combination of in situ and satellite derived radiometric measurements and a modified version of the General Ocean Turbulence Model (GOTM), which includes the National Oceanic and Atmospheric Administration Coupled-Ocean Atmospheric Response Experiment (NOAA-COARE) air–sea gas transfer parameterization, to investigate heat and carbon dioxide exchange over the diurnal cycle in the Tropical Atlantic. A new term based on a water-side convective velocity scale (w_*w) is included, to improve parameterization of convectively driven gas transfer. Meteorological data from the PIRATA mooring located at 10°S10°W in the Tropical Atlantic are used, in conjunction with cloud cover estimates from Meteosat-7, to calculate fluxes of longwave, latent and sensible heat along with a heat budget and temperature profiles during February 2002. Twin model experiments, representing idealistic and realistic conditions, reveal that over daily time scales the additional contribution to gas exchange from convective overturning is important. Increases in transfer velocity of up to 20% are observed during times of strong insolation and low wind speeds (<6 m s⁻¹); the greatest enhancement from w_*w to the CO₂ flux occurs when diurnal warming is large. Hence, air–sea fluxes of CO₂ calculated using simple parameterizations underestimate the contribution from convective processes. The results support the need for parameterizations of gas transfer that are based on more than wind speed alone and include information about the heat budget.     

Occurrence of an exceptional carbonate dissolution episode during early glacial isotope stage 6 in the Southeastern Atlantic

Concentration and mass accumulation rate profiles from Southeastern Atlantic sediment cores located off Namibia show that an exceptional episode in benthic carbonate dissolution occurred during early glacial isotope stage 6 (substages 6.6 and 6.5) between about 186 000 and 170 000 yr BP. Although this episode is restricted to or is more pronounced in this region than in other areas of the Atlantic Ocean, its exceptional character with respect to older and younger climatic episodes at the same site cannot be fully explained by local factors alone, but requires a combination of local and global influences. The onset of the carbonate dissolution episode is related to a more efficient transfer of organic matter from surface eutrophic areas to the lower and is due to low sea level, while its termination relates to a change in either global ocean alkalinity or bottom water circulation. An evaluation of the magnitude of this local carbonate dissolution episode suggests that its contribution to a global alkalinity change may have been significant. Carbonate dissolution was probably amplified by stronger upwelling activity of the Benguela System linked to an exceptional northern excursion of the boreal summer ITCZ during early glacial isotope stage 6. This low latitude global linkage may explain how this carbonate dissolution event as well as other ‘anomalies’ observed for early stage 6, like an important Dole effect minimum or a ‘cold’ Mediterranean sapropel, are related.     

Rainfall effect on wind waves and the turbulence beneath air-sea interface

Rainfall effects on wind waves and turbulence are investigated through the laboratory experiments in a large wind-wave tank. It is found that the wind waves are damped as a whole at low wind speeds, but are enhanced at high wind speeds. This dual effect of rain on the wind waves increases with the increase of rain rate, while the influence of rainfall-area length is not observable. At the low wind speed, the corresponding turbulence in terms of the turbulent kinetic energy （TKE） dissipation rate is significantly enhanced by rain- fall as the waves are damped severely. At the high wind speed, the augment of the TKE dissipation rate is suppressed while the wind waves are enhanced simultaneously. In the field, however, rainfall usually hin- ders the development of waves. In order to explain this contradiction of rainfall effect on waves, a possibility about energy transfer from turbulence to waves in case of the spectral peak of waves overlapping the inertial subrange of turbulence is assumed. It can be applied to interpret the damping phenomenon of gas trans- fer velocity in the laboratory experiments, and the variation of the TKE dissipation rates near sea surface compared with the law of wall.     

南海深水区水下溢油三维可视化模拟系统研发与应用

针对南海油气田勘探开发溢油污染防治需求,开发了国内首套深水区水下溢油三维可视化模拟系统,由三维海流预报模型、深水溢油模型、三维可视化仿真系统和数据库组成。海流预报模型基于ROMS模式,通过考虑波致混合影响,并利用最优插值技术同化卫星测高资料和嵌套技术,保障了预报结果的准确性。深水溢油模型由羽流模型和对流扩散模型组成,考虑了卷吸、油气分离、溶解、水合物生成、漂移、扩散等复杂过程。系统能够预测深水区水下油气泄漏后行为和归宿过程,提供油、气、天然气水合物粒子的大小、分布、移动速度和漂移轨迹、扩散面积、水体溢油残存量、水面溢油量等三维可视化动态模拟结果。目前系统已经在油气田勘探开发中得到应用,为南海深水溢油应急提供了重要支撑。     

Biological controls on dissolution of diatom frustules during their descent to the deep ocean: Lessons learned from controlled laboratory experiments

The majority of opal produced by diatoms dissolves during their sedimentation to the seafloor, but spatial and temporal variability of dissolution rates are large. Controlled laboratory experiments using live phytoplankton or phyto-detritus may help identify the different processes, including those that are biologically mediated or physico-chemically driven, that impact the dissolution of frustules and the aforementioned variability. Results of eight bSiO₂ dissolution experiments, seven of which were conducted at low temperatures (<6 °C) are presented within the context of earlier similar studies, and different phases of dissolution dynamics characterized. TEP concentration, aggregation and the physiological status of the diatoms determined the period during which diatoms may maintain the protective membrane that surrounds their frustule and effectively reduces or completely inhibits (lag period) dissolution for some time. Once diatoms loose the capability to maintain their protective membrane, bacterial activity compromises it. Physico-chemical dissolution, which depends on frustule structure and abiotic environmental conditions, begins once the protective membrane is damaged. The ability of diatoms to maintain their membrane, the bacterial composition and activity governing its degradation, and the physico-chemical dissolution dynamics of exposed frustules are all impacted by temperature. In our experiments instantaneous dissolution rates were not dependant on bSiO₂ concentration at low temperatures, although such a relationship was observed under otherwise identical conditions at 15 °C, implying that biotic factors rather than physico-chemical processes initially dominated dissolution at polar temperatures. Since inhibition of bSiO₂ dissolution at low temperatures was inhibited to a greater extent than organic matter degradation, we postulate that it was not reduced bacterial activity but the enhanced ability of diatoms to maintain their membrane and thus withstand microbial attack that caused the low initial dissolution rates at <6 °C. In situ, interactions between the different biotic and abiotic processes impacting dissolution combined with differences in sinking velocity of diatom aggregates and grazing effects could easily explain high spatial and temporal variability in the accumulation of diatoms on the seafloor. Simple calculations based on our experimental results suggest that Fragilariopsis kerguelensis, for example, would be appreciably more likely to reach the seafloor than Chaetoceros debilis if both grow at low growth rates, e.g. under growth limiting conditions. However, dissolution behavior of Chaetoceros debilis during sedimentation may differ under conditions where this species forms large blooms.     

Effect of siderophores on the light-induced dissolution of colloidal iron(III) (hydr)oxides

Siderophores play an important role in biological iron acquisition in iron-limited aquatic systems. While it is widely accepted that the solubilization of iron-bearing mineral phases is a key function of siderophores, the mechanism of siderophore-promoted mineral dissolution in aquatic systems is largely unknown. In this study, we investigated the effect of siderophores (desferrioxamine B (DFOB) and aerobactin) on light-induced dissolution of goethite and lepidocrocite in the presence or absence of oxalate in aerated and deaerated suspensions at pH 6. For the irradiated two-ligand system (oxalate/siderophore), the experimental results suggest that oxalate acts as the electron donor for the formation of surface Fe(II), and the siderophore acts as an efficient shuttle for the transfer of surface Fe(II) into solution. Furthermore, even in the absence of an electron donor such as oxalate, both DFOB and aerobactin accelerated the light-induced dissolution of lepidocrocite as compared to the thermal dissolution. Experiments with dissolved Fe(III)–DFOB and Fe(III)–aerobactin complexes suggest that this enhancing effect is not due to photolysis of corresponding surface complexes but to efficient transfer of reduced surface Fe(II) into solution, where surface Fe(II) may be formed, e.g., through photolysis of surface Fe(III)–hydroxo groups. Based on this study, we conclude that the interplay of light and siderophores may play a key role in the dissolution of colloidal iron(III) (hydr)oxides in marine systems, particularly in the presence of efficient electron donors.     

基于高斯烟羽模型的船舶尾气扩散研究

为有效对港区大气污染进行治理、分析船舶尾气,本文详细介绍了一种基于高斯烟羽模型,通过MATLAB模拟仿真模型,其包括实验仿真过程、技术原理及理论模型对船舶尾气扩散进行的研究。该模型是在传统的高斯烟羽模型的基础上,通过对实源像源进行加权选择输入参数;通过矢量合成确定了气体扩散的方向,利用合成后的"风速"进行计算仿真,有效模拟了船舶尾气在港区或者海洋环境中的气体扩散模型。其模型简单且可以有效模拟船舶尾气扩散。并且进一步对后续模型的精确优化进行分析。     

Transport of the colloid matter of riverine runoff through estuaries

A procedure for separating the colloid component of natural waters is proposed. It was shown that this component is the main form of matter transfer in Ob River runoff, because the mass of colloid substance is two orders of magnitude higher than that of particulate matter in the outer part of the estuary. Simulation and field experiments revealed the influence of nature and concentration of organic matter on their ability to stabilize or flocculate clay particles with an increase in salinity, thus affecting the range of transfer of riverine runoff matter. It was shown that the interaction of humic acids and clay particles, as well as the increase in hydrophobic properties of a flocculant, improve flocculation efficiency. Criteria are proposed to recognize in the estuarine region areas of pronounced contribution of flocculation processes to sedimentation of fine particles. It is shown that the newly formed organic matter produced by biota under saline stress might be flocculants of fine particulate matter.     

吸附式制冷单管吸附床传热传质的数值模拟及分析

建立氯化钙—氨吸附式制冷单管吸附床传热传质模型 ,采用数值方法对该模型进行了求解 ,得出不同工况下的温度场 ,讨论了吸附床的有效导热系数、接触热阻、流体传热系数等对解吸量及制冷功率的影响。结果表明 ,提高吸附床导热有效导热系数 ,减小接触热阻可有效地改善吸附床的性能 ,为吸附床的优化设计提供了依据     

An experiment demonstrating that marine slumping is a mechanism to transfer methane from seafloor gas-hydrate deposits into the upper ocean and atmosphere

The scientific community is engaged in a lively debate over whether and how venting from the gas-hydrate reservoir and the Earth’s climate is connected. The various scenarios which have been proposed are based on the following assumptions: the inventory of methane gas-hydrate deposits is locally enormous, the stability of marine gas-hydrate deposits can easily be perturbed by temperature and pressure changes, enough methane can be released from these deposits to contribute adequate volumes of this isotopically distinct greenhouse gas to alter the composition of oceanic or atmospheric methane reservoirs, and the mechanisms exist for the transfer of methane from deeper geologic reservoirs to the ocean and/or atmosphere. However, some potential transfer mechanisms have been difficult to evaluate. Here, we consider the possibility of marine slumping as a mechanism to transfer methane carbon from gas hydrates within the seafloor into the ocean and atmosphere. Our analyses and field experiments indicate that large slumps could release volumetrically significant quantities of solid gas hydrates which would float upwards in the water column. Large pieces of gas hydrate would reach the upper layers of the ocean before decomposing, and some of the methane would be directly injected into the atmosphere.     

Critical evaluation of an Upper Carboniferous tight gas sandstone reservoir analog: Diagenesis and petrophysical aspects

Upper Carboniferous sandstones are one of the most important tight gas reservoirs in Central Europe. We present data from an outcrop reservoir analog (Piesberg quarry) in the Lower Saxony Basin of Northern Germany. This field-based study focuses on the diagenetic control on spatial reservoir quality distribution.The investigated outcrop consists of fluvial 4^th-order cycles, which originate from a braided river dominated depositional environment. Westphalian C/D stratigraphy, sedimentary thicknesses and exposed fault orientations (NNW-SSE and W-E) reflect tight gas reservoir properties in the region further north. Diagenetic investigations revealed an early loss of primary porosity by pseudomatrix formation. Present day porosity (7% on average) and matrix permeability (0.0003 mD on average) reflect a high-temperature overprint during burial. The entire remaining pore space is occluded with authigenic minerals, predominantly quartz and illite. This reduces reservoir quality and excludes exposed rocks as tight gas targets. The correlation of petrographic and petrophysical data show that expected facies-related reservoir quality trends were overprinted by high-temperature diagenesis. The present day secondary matrix porosity reflects the telogenetic dissolution of mesogenetic ankerite cements and unstable alumosilicates.Faults are associated with both sealed and partially sealed veins near the faults, indicating localized mass transport. Around W-E striking faults, dissolution is higher in leached sandstones with matrix porosities of up to 26.3% and matrix permeabilities of up to 105 mD. The dissolution of ankerite and lithic fragments around the faults indicates focused fluid flow. However, a telogenetic origin cannot be ruled out.The results of this work demonstrate the limits of outcrop analog studies with respect to actual subsurface reservoirs of the greater area. Whereas the investigated outcrop forms a suitable analog with respect to sedimentological, stratigraphic and structural inventory, actual reservoirs at depth generally lack telogenetic influences. These alter absolute reservoir quality values at the surface. However, the temperature overprint and associated diagenetic modification, which caused the unusually low permeability in the studied outcrop, may pose a reservoir risk for tight gas exploration as a consequence of locally higher overburden or similar structural positions.