Showing papers on "Methane published in 2007"

Oceanic methane biogeochemistry.

Abstract: This review shows that thermodynamic and kinetic constraints largely prevent large-scale methanogenesis in the open ocean water column. One example of open-ocean methanogenesis involves anoxic digestive tracts and fecal pellet microenvironments; methane released during fecal pellet disaggregation results in the mixed-layer methane maximum. However, the bulk of the methane in the ocean is added by coastal runoff, seeps, hydrothermal vents, decomposing hydrates, and mud volcanoes. Since methane is present in the open ocean at nanomolar concentrations, and since the flux to the atmosphere is small, the ultimate fate of ocean methane additions must be oxidation within the ocean. As indicated in the Introduction and highlighted in Table 3, sources of methane to the ocean water column are poorly quantified. There are only a small number of direct water column methane oxidation rates, so sinks are also poorly quantified. We know that methane oxidation rates are sensitive to ambient methane concentrations, but we have no information on reaction kinetics and only one report of the effect of pressure on methane oxidation. Our perspective on methane sources and the extent of methane oxidation has been changed dramatically by new techniques involving gene probes, determination of isotopically depleted biomarkers, and recent 14C-CH4 measurements showing that methane geochemistry in anoxic basins is dominated by seeps providing fossil methane. The role of anaerobic oxidation of methane has changed from a controversial curiosity to a major sink in anoxic basins and sediments. © 2007 American Chemical Society.

Microbial Ecology of Methanogens and Methanotrophs

Abstract: Rice agriculture feeds about a third of the world's population. However, rice fields are also an important source in the global budget of the greenhouse gas methane. The emission of methane from flooded rice fields is the result of the activity of methanogenic archaea that produce the methane and of methanotrophic bacteria that oxidize part of it, so that the ecology of these two physiological groups of microorganisms is key for the understanding of methane cycling in rice fields and for possible mitigation of emission from this important agro-ecosystem. In this chapter I will describe the ecology of methanogens and methanotrophs and will give examples where production and emission of methane on the field scale can be understood on the basis of processes on the microscale.

Shale Gas Potential of the Lower Jurassic Gordondale Member, Northeastern British Columbia, Canada

Abstract: The Lower Jurassic Gordondale Member is an organic-rich mudrock and is widely considered to have potential as a shale gas reservoir. Influences of Gordondale mudrock composition on total gas capacities (sorbed and free gas) have been determined to assess the shale gas resource potential of strata in the Peace River district, northeastern British Columbia. Sorbed gas capacities of moisture-equilibrated samples increase over a range of 0.5 to 12 weight percent total organic carbon content (TOC). Methane adsorption capacities range from 0.05 cc/g to over 2 cc/g in organic-rich zones (at 6 MPa and 30°C). Sorption capacities of mudrocks under dry conditions are greater than moisture equilibrated conditions due to water occupation of potential sorption sites. However, there is no consistent decrease of sorption capacity with increasing moisture as the relationship is masked by both the amount of organic matter and thermal maturation level. Clays also affect total gas capacities in as much as clay-rich mudrocks have high porosity which may be available for free gas. Gordondale samples enriched with carbonate (calcite and dolomite) typically have lower total porosities than carbonate-poor rocks and hence have lower potential free gas contents. On a regional reservoir scale, a large proportion of the Gordondale total gas capacity is free gas storage (intergranular porosity), ranging from 0.1-22 Bcf/section (0.003-0.66 m3/section). Total gas-in-place capacity ranges from 1-31.4 Bcf/section (0.03-0.94 m3/section). The greatest potential for gas production is in the south of the study area (93-P) due to higher thermal maturity, TOC enrichment, higher reservoir pressure, greater unit thickness and improved fracture-potential.

Hydrogen and Methane Adsorption in Metal−Organic Frameworks: A High-Pressure Volumetric Study

Abstract: We report hydrogen and methane adsorption isotherms in two prototypical metal−organic framework compounds (i.e., MOF5 and ZIF8) over a large temperature (30−300 K) and pressure (up to 65 bar) range using a fully computer-controlled Sieverts apparatus. We find that, in a volumetric method, a proper choice of real gas equation of state is critical for obtaining reliable isotherm data. The widely used van der Waals equation of state (EOS) is not adequate to describe H2 and CH4, while the modified Benedict−Webb−Rubin (MBWR) EOS works well, even at very low temperatures and high pressures. With the known sample mass and bulk density, the skeleton density and the specific pore volume of MOF5 and ZIF8 were also measured. In addition to excess and absolute adsorption isotherms, we also introduce an “effective adsorption” which compares the amounts of gas adsorbed in a container with and without the adsorbent. At low temperatures, the maximal excess adsorption capacities of H2 and CH4 in MOF5 are found to be 10.3 ...

Methane hydrate stability and anthropogenic climate change

Abstract: . Methane frozen into hydrate makes up a large reservoir of potentially volatile carbon below the sea floor and associated with permafrost soils. This reservoir intuitively seems precarious, because hydrate ice floats in water, and melts at Earth surface conditions. The hydrate reservoir is so large that if 10% of the methane were released to the atmosphere within a few years, it would have an impact on the Earth's radiation budget equivalent to a factor of 10 increase in atmospheric CO2. Hydrates are releasing methane to the atmosphere today in response to anthropogenic warming, for example along the Arctic coastline of Siberia. However most of the hydrates are located at depths in soils and ocean sediments where anthropogenic warming and any possible methane release will take place over time scales of millennia. Individual catastrophic releases like landslides and pockmark explosions are too small to reach a sizable fraction of the hydrates. The carbon isotopic excursion at the end of the Paleocene has been interpreted as the release of thousands of Gton C, possibly from hydrates, but the time scale of the release appears to have been thousands of years, chronic rather than catastrophic. The potential climate impact in the coming century from hydrate methane release is speculative but could be comparable to climate feedbacks from the terrestrial biosphere and from peat, significant but not catastrophic. On geologic timescales, it is conceivable that hydrates could release as much carbon to the atmosphere/ocean system as we do by fossil fuel combustion.

Anaerobic oxidation of short-chain hydrocarbons by marine sulphate-reducing bacteria

Abstract: There has been an increasing interest in organisms thriving at marine gas seeps, in particular microbes that utilize methane. Surprisingly, there seems to have been comparatively little work done on the fate of the other abundant hydrocarbons in natural gases — ethane, propane and butane. Now sediments collected from hydrocarbon seep areas in the Gulf of Mexico and the Gulf of California have yielded microbial cultures that utilize propane and butane under anoxic conditions similar to those prevailing in gas reservoirs. These biochemically unusual bacteria may be responsible for the observed alteration of gases in seeps and other gas reservoirs. Ethane, propane and butane are constituents of natural gas in anoxic marine sediments. The first microbial isolate belonging to the sulphate-reducing bacteria capable of anaerobically oxidizing short-chain non-methane hydrocarbons is described. The short-chain hydrocarbons ethane, propane and butane are constituents of natural gas. They are usually assumed to be of thermochemical origin1, but biological formation of ethane and propane has been also observed2. Microbial utilization of short-chain hydrocarbons has been shown in some aerobic species3,4 but not in anaerobic species of bacteria. On the other hand, anaerobic utilization of short-chain hydrocarbons would in principle be expected because various anaerobic bacteria grow with higher homologues (≥C6)5. Indeed, chemical analyses of hydrocarbon-rich habitats with limited or no access of oxygen indicated in situ biodegradation of short-chain hydrocarbons6,7,8,9,10. Here we report the enrichment of sulphate-reducing bacteria (SRB) with such capacity from marine hydrocarbon seep areas. Propane or n-butane as the sole growth substrate led to sediment-free sulphate-reducing enrichment cultures growing at 12, 28 or 60 °C. With ethane, a slower enrichment with residual sediment was obtained at 12 °C. Isolation experiments resulted in a mesophilic pure culture (strain BuS5) that used only propane and n-butane (methane, isobutane, alcohols or carboxylic acids did not support growth). Complete hydrocarbon oxidation to CO2 and the preferential oxidation of 12C-enriched alkanes were observed with strain BuS5 and other cultures. Metabolites of propane included iso- and n-propylsuccinate, indicating a subterminal as well as an unprecedented terminal alkane activation with involvement of fumarate. According to 16S ribosomal RNA analyses, strain BuS5 affiliates with Desulfosarcina/Desulfococcus, a cluster of widespread marine SRB. An enrichment culture with propane growing at 60 °C was dominated by Desulfotomaculum-like SRB. Our results suggest that diverse SRB are able to thrive in seep areas and gas reservoirs on propane and butane, thus altering the gas composition and contributing to sulphide production.

Oceanic Methane Biogeochemistry

Abstract: This review shows that thermodynamic and kinetic constraints largely prevent large-scale methanogenesis in the open ocean water column. One example of open-ocean methanogenesis involves anoxic digestive tracts and fecal pellet microenvironments; methane released during fecal pellet disaggregation results in the mixed-layer methane maximum. However, the bulk of the methane in the ocean is added by coastal runoff, seeps, hydrothermal vents, decomposing hydrates, and mud volcanoes. Since methane is present in the open ocean at nanomolar concentrations, and since the flux to the atmosphere is small, the ultimate fate of ocean methane additions must be oxidation within the ocean. As indicated in the Introduction and highlighted in Table 3, sources of methane to the ocean water column are poorly quantified. There are only a small number of direct water column methane oxidation rates, so sinks are also poorly quantified. We know that methane oxidation rates are sensitive to ambient methane concentrations, but we have no information on reaction kinetics and only one report of the effect of pressure on methane oxidation. Our perspective on methane sources and the extent of methane oxidation has been changed dramatically by new techniques involving gene probes, determination of isotopically depleted biomarkers, and recent 14C-CH4 measurements showing that methane geochemistry in anoxic basins is dominated by seeps providing fossil methane. The role of anaerobic oxidation of methane has changed from a controversial curiosity to a major sink in anoxic basins and sediments. © 2007 American Chemical Society.

Global budget of CO, 1988–1997: Source estimates and validation with a global model

Abstract: [1] We present a model study of carbon monoxide for 1988–1997 using the GEOS-Chem 3-D model driven by assimilated meteorological data, with time-varying emissions from biomass burning and from fossil fuel and industry, overhead ozone columns, and methane. The hydroxyl radical is calculated interactively using a chemical parameterization to capture chemical feedbacks. We document the inventory for fossil fuels/industry and discuss major uncertainties and the causes of differences with other inventories that give significantly lower emissions. We find that emissions hardly change from 1988 to 1997, as increases in Asia are offset by decreases elsewhere. The model reproduces the 20% decrease in CO at high northern latitudes and the 10% decrease in the North Pacific, caused primarily by the decrease in European emissions. The model compares well with observations at sites impacted by fossil fuel emissions from North America, Europe, and east Asia suggesting that the emissions from this source are reliable to 25%, and we argue that bottom-up emission estimates are likely to be too low rather than too high. The model is too low at the seasonal maximum in spring in the southern tropics, except for locations in the Atlantic Ocean. This problem may be caused by an overestimate of the frequency of tropical deep convection, a common problem in models that use assimilated meteorological data. We argue that the yield of CO from methane oxidation is near unity, contrary to some other studies, based on removal rates of intermediate species.

Equilibrium Data of Hydrogen, Methane, Nitrogen, Carbon Dioxide, and Natural Gas in Semi-Clathrate Hydrates of Tetrabutyl Ammonium Bromide

Abstract: Tetrabutyl ammonium bromide (TBAB) forms a semi-clathrate hydrate, which can incorporate small gas molecules such as methane and nitrogen. It has recently been used for separation of gases. However, there are very limited experimental data on the phase boundaries of the gas hydrate form in the presence of TBAB. In this work, we present new experimental data at high-pressure TBAB, w = 0.10, TBAB (w = 0.10 and 0.43) + hydrogen, TBAB (w = 0.05, 0.10, 0.20, and 0.30) + methane, TBAB (w = 0.10) + nitrogen, TBAB (w = 0.1 and 0.427) + carbon dioxide, and TBAB (w = 0.05, 0.10, and 0.43) + natural gas semi-clathrate hydrate phase boundaries. In another part of this work, the results of visual observations of the methane + TBAB semi-clathrate hydrate morphology and the methane gas bubbles released from methane + TBAB semi-clathrate hydrates on dissociation are presented. Finally, the effect of TBAB mass fraction on hydrate promotion and the stability of the new semi-clathrate hydrate are presented.

Large-eddy simulation and experimental study of heat transfer, nitric oxide emissions and combustion instability in a swirled turbulent high-pressure burner

Abstract: Nitric oxide formation in gas turbine combustion depends on four key factors: flame stabilization, heat transfer, fuel–air mixing and combustion instability. The design of modern gas turbine burners requires delicate compromises between fuel efficiency, emissions of oxides of nitrogen (NOx) and combustion stability. Burner designs allowing substantial NOx reduction are often prone to combustion oscillations. These oscillations also change the NOx fields. Being able to predict not only the main species field in a burner but also the pollutant and the oscillation levels is now a major challenge for combustion modelling. This must include a realistic treatment of unsteady acoustic phenomena (which create instabilities) and also of heat transfer mechanisms (convection and radiation) which control NOx generation.In this work, large-eddy simulation (LES) is applied to a realistic gas turbine combustion chamber configuration where pure methane is injected through multiple holes in a cone-shaped burner. In addition to a non-reactive simulation, this article presents three reactive simulations and compares them to experimental results. The first reactive simulation neglects effects of cooling air on flame stabilization and heat losses by radiation and convection. The second reactive simulation shows how cooling air and heat transfer affect nitric oxide emissions. Finally, the third reactive simulation shows the effects of combustion instability on nitric oxide emissions. Additionally, the combustion instability is analysed in detail, including the evaluation of the terms in the acoustic energy equation and the identification of the mechanism driving the oscillation.Results confirm that LES of gas turbine combustion requires not only an accurate chemical scheme and realistic heat transfer models but also a proper description of the acoustics in order to predict nitric oxide emissions and pressure oscillation levels simultaneously.

Complex gas hydrate from the Cascadia margin

Abstract: Natural gas hydrates — ice-like solids that consist of 'guest' molecules trapped in cages of water molecules — are a potential source of energy and may play a role in climate change and seafloor collapse. Experiments have shown that there are three common gas hydrate structures — sI, sII and sH — but only sI and sII hydrate have been found in the natural environment. Now sH hydrate (in close association with sII hydrate) has been identified in seafloor samples from Barkley canyon, 80 km off Vancouver Island. This complex gas hydrate can trap larger guest molecules than sI or sII, and is more stable than sI hydrate, indicating that gas hydrates could be more widely distributed than previously thought. The discovery of sH hydrate in a sample from Barkley Canyon marks the first time this hydrate has been found in the natural environment. This complex gas hydrate can trap larger guest molecules than sI or sII hydrate, and is stable at higher temperatures and pressures than sI hydrate, indicating that gas hydrates could be more widely distributed than previously thought. Natural gas hydrates are a potential source of energy1 and may play a role in climate change2 and geological hazards3. Most natural gas hydrate appears to be in the form of ‘structure I’, with methane as the trapped guest molecule4, although ‘structure II’ hydrate has also been identified, with guest molecules such as isobutane and propane, as well as lighter hydrocarbons5,6. A third hydrate structure, ‘structure H’, which is capable of trapping larger guest molecules, has been produced in the laboratory7, but it has not been confirmed that it occurs in the natural environment. Here we characterize the structure, gas content and composition, and distribution of guest molecules in a complex natural hydrate sample recovered from Barkley canyon, on the northern Cascadia margin8. We show that the sample contains structure H hydrate, and thus provides direct evidence for the natural occurrence of this hydrate structure. The structure H hydrate is intimately associated with structure II hydrate, and the two structures contain more than 13 different hydrocarbon guest molecules. We also demonstrate that the stability field of the complex gas hydrate lies between those of structure II and structure H hydrates, indicating that this form of hydrate is more stable than structure I and may thus potentially be found in a wider pressure–temperature regime than can methane hydrate deposits.

Dynamic multiphase flow model of hydrate formation in marine sediments

Abstract: [1] We developed a multicomponent, multiphase, fluid and heat flow model to describe hydrate formation in marine sediments; the one- and two-dimensional model accounts for the dynamic effects of hydrate formation on salinity, temperature, pressure, and hydraulic properties. Free gas supplied from depth forms hydrate, depletes water, and elevates salinity until pore water is too saline for further hydrate formation: Salinity and hydrate concentration increase upward from the base of the regional hydrate stability zone (RHSZ) to the seafloor, and the base of the hydrate stability zone has significant topography. In fine-grained sediments, hydrate formation leads to rapid permeability reduction and capillary sealing to free gas. This traps gas and causes gas pressure to build up until it exceeds the overburden stress and drives gas through the RHSZ. Gas chimneys couple the free gas zone to the seafloor through high-salinity conduits that are maintained at the three-phase boundary by gas flow. As a result, significant amounts of gaseous methane can bypass the RHSZ, which implies a significantly smaller hydrate reservoir than previously envisioned. Hydrate within gas chimneys lies at the three-phase boundary, and thus small increases in temperature or decreases in pressure can immediately transport methane into the ocean. This type of hydrate deposit may be the most economical for producing energy because it has very high methane concentrations (Sh > 70%), located near the seafloor, which lie on the three-phase boundary.

Annual cycle of methane emission from a boreal fen measured by the eddy covariance technique

Abstract: The northern wetlands are one of the major sources of methane into the atmosphere. We measured annual methane emission from a boreal minerotrophic fen, Siikaneva, by the eddy covariance method. The average wintertime emissions were below 1 mg m -2 h -1 , and the summertime emissions about 3.5 mg m -2 h -1 . The water table depth did have any clear effect on methane emissions. During most of the year the emission depended on the temperature of peat below the water table. However, during the high and late summer the emission was independent on peat temperature as well. No diurnal cycle of methane flux was found. The total annual emission from the Siikaneva site was 12.6 g m -2 . The emissions of the snow free period contributed 91% to the annual emission. The emission pulse during the snow melting period was clearly detectable but of minor importance adding only less than 3% to the annual emission. Over 20% of the carbon assimilated during the year as carbon dioxide was emitted as methane. Thus methane emission is an important component of the carbon balance of the Siikaneva fen. This indicates need of taking methane into account when studying carbon balances of northern fen ecosystems. DOI: 10.1111/j.1600-0889.2007.00261.x

Adsorption-induced coal swelling and stress: Implications for methane production and acid gas sequestration into coal seams

Abstract: [1] Sequestration of CO2 and H2S into deep unminable coal seams is an attractive option to reduce their emission into atmosphere and at the same time displace preadsorbed CH4 which is a clean energy resource. High coal seam permeability is required for efficient and practical sequestration of CO2 and H2S and recovery of CH4. However, adsorption of CO2 and H2S into coals induces strong swelling of the coal matrix (volumetric strain) and thus reduces significantly coal permeability by narrowing and even closing fracture apertures. Our experimental data on three western Canadian coals show that the adsorption-induced volumetric strain is approximately linearly proportional to the volume of adsorbed gas, and for the same gas, different coals have very similar volumetric strain coefficient. Impacts of adsorption-induced swelling on stress and permeability around wellbores were analytically investigated using our developed stress and permeability models. Our model results indicate that adsorption-induced volumetric strain has significant controls on stress and permeability of producing and sequestrating coal seams and consequently the potential of acid gas sequestration. Coal seams may undergo >10 times enhancement of permeability around CH4-producing wellbores due to a reduction in effective stress as a result of coal shrinking caused by methane desorption accompanying a reduction in reservoir pressure. Injection of H2S and CO2 on the other hand results in strong sorption-induced swelling and a marked increase in effective stress which in turn leads to a reduction of coal seam permeability of up to several orders of magnitude. Injection of mixtures of N2 and CO2 such as found in flue gas results in weaker swelling, the amount of which varies with gas composition, and provides the greatest opportunity of sequestering CO2 and secondary recovery of CH4 for most coals. Because of the marked swelling of coal in the presence of H2S, even minor amounts of H2S result in a marked reduction in permeability, and hence sequestration of H2S in deep coals will be likely impractical. Furthermore, high stresses resulting from sorption of acid gases will potentially cause the coal to yield, fracture or slip, and produce fine particles, which further affect permeability and thus methane production and acid gas sequestration.

Application of a modified Dubinin-Radushkevich equation to adsorption of gases by coals under supercritical conditions

Abstract: The classic Dubinin−Radushkevich (DR) equation, which is used to describe the adsorption of gases, requires a “saturation pressure” in its calculation, which is not defined for supercritical conditions. By using gas density instead of gas pressure (and adsorbed phase density rather than saturation pressure) to describe the sorption of the gas onto the surface, the DR equation can be applied in supercritical conditions. A proportionality term (k times the gas density) was added to this modified DR equation to account for possibilities such as Henry's law dissolution by the coal, errors in cell volume and helium density, and differences in the accessibility to coal between helium and the other gases. The sorption characteristics of three dry Australian bituminous coals when exposed to carbon dioxide, methane, and nitrogen were measured over the range 0−20 MPa at 53 °C. The data were fitted by the modified DR equation to within 1% of the sorption capacity across the isotherm in nearly all cases, substantiall...

Characterization of surface processes at the Ni-based catalyst during the methanation of biomass-derived synthesis gas: X-ray photoelectron spectroscopy (XPS)

Abstract: Surface modifications during the production of methane from reformer synthesis gas over a commercial Ni/Al2O3 catalyst were investigated by quasi-in situ X-ray photoelectron spectroscopy (XPS) and other surface analytical techniques. Experiments of methanation reaction were done in the high pressure cell (HPC) integrated in the XPS system and under fixed-bed conditions. The interaction of the different reformer biomass-derived synthesis gas on the surface properties of the catalyst and on its activity under methanation conditions were studied on a nanoscopic level. Detailed description of changes in metal particle morphology and carbon deposit is presented. A mechanism of C-whiskers formation during long exposure to methanation conditions is described. The role of additional components in the gas mixture, such as CO2, H2O, CH4, C2H4, C2H2, C3H6 and C2H6, were studied in details. Furthermore, role of different nickel compounds such as oxides, hydroxides, carbides and carbonates are discussed.