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Showing papers on "Methane published in 2015"


Journal ArticleDOI
09 Apr 2015-Nature
TL;DR: In this paper, the authors find that current evidence suggests a gradual and prolonged release of greenhouse gas emissions in a warming climate and present a research strategy with which to target poorly understood aspects of permafrost carbon dynamics.
Abstract: Large quantities of organic carbon are stored in frozen soils (permafrost) within Arctic and sub-Arctic regions. A warming climate can induce environmental changes that accelerate the microbial breakdown of organic carbon and the release of the greenhouse gases carbon dioxide and methane. This feedback can accelerate climate change, but the magnitude and timing of greenhouse gas emission from these regions and their impact on climate change remain uncertain. Here we find that current evidence suggests a gradual and prolonged release of greenhouse gas emissions in a warming climate and present a research strategy with which to target poorly understood aspects of permafrost carbon dynamics.

2,282 citations


Journal ArticleDOI
19 Nov 2015-Nature
TL;DR: Flexible compounds Fe(bdp) and Co(BDp) (bdp2− = 1,4-benzenedipyrazolate) are shown to undergo a structural phase transition in response to specific CH4 pressures, resulting in adsorption and desorption isotherms that feature a sharp ‘step’.
Abstract: Two flexible metal-organic frameworks are presented as solid adsorbents for methane that undergo reversible phase transitions at specific methane pressures, enabling greater storage capacities of usable methane than have been achieved previously, while also providing internal heat management of the system. Natural gas — methane — is a clean and cheap fuel but its usefulness in transport applications is limited by storage problems, given its low energy density per unit volume under ambient conditions compared with petrol or diesel. One way of increasing methane storage capacity is to use tanks containing porous materials, such as metal–organic frameworks, as a storage medium. However, for every methane molecule adsorbed and desorbed there is an associated thermal fluctuation that could cause overheating or reduce storage efficiency if left unchecked. Here Jeffrey Long and colleagues describe two flexible metal–organic frameworks that undergo reversible phase transitions at specific methane pressures, enabling greater storage capacities of usable methane than have been achieved previously, while also providing internal heat management of the system. As a cleaner, cheaper, and more globally evenly distributed fuel, natural gas has considerable environmental, economic, and political advantages over petroleum as a source of energy for the transportation sector1,2. Despite these benefits, its low volumetric energy density at ambient temperature and pressure presents substantial challenges, particularly for light-duty vehicles with little space available for on-board fuel storage3. Adsorbed natural gas systems have the potential to store high densities of methane (CH4, the principal component of natural gas) within a porous material at ambient temperature and moderate pressures4. Although activated carbons, zeolites, and metal–organic frameworks have been investigated extensively for CH4 storage5,6,7,8, there are practical challenges involved in designing systems with high capacities and in managing the thermal fluctuations associated with adsorbing and desorbing gas from the adsorbent. Here, we use a reversible phase transition in a metal–organic framework to maximize the deliverable capacity of CH4 while also providing internal heat management during adsorption and desorption. In particular, the flexible compounds Fe(bdp) and Co(bdp) (bdp2− = 1,4-benzenedipyrazolate) are shown to undergo a structural phase transition in response to specific CH4 pressures, resulting in adsorption and desorption isotherms that feature a sharp ‘step’. Such behaviour enables greater storage capacities than have been achieved for classical adsorbents9, while also reducing the amount of heat released during adsorption and the impact of cooling during desorption. The pressure and energy associated with the phase transition can be tuned either chemically or by application of mechanical pressure.

737 citations


Journal ArticleDOI
TL;DR: The mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon–hydrogen bonds in methane and its subsequent transformation to methanol.
Abstract: Copper-exchanged zeolites with mordenite structure mimic the nuclearity and reactivity of active sites in particulate methane monooxygenase, which are enzymes able to selectively oxidize methane to methanol. Here we show that the mordenite micropores provide a perfect confined environment for the highly selective stabilization of trinuclear copper-oxo clusters that exhibit a high reactivity towards activation of carbon–hydrogen bonds in methane and its subsequent transformation to methanol. The similarity with the enzymatic systems is also implied from the similarity of the reversible rearrangements of the trinuclear clusters occurring during the selective transformations of methane along the reaction path towards methanol, in both the enzyme system and copper-exchanged mordenite.

565 citations


Journal ArticleDOI
TL;DR: In this article, the authors present a review of recent results and developments in heterogeneous catalytic methane conversion to synthesis gas, hydrogen cyanide, ethylene, methanol, formaldehyde, methyl chloride, methyl bromide and aromatics.
Abstract: Methane activation by heterogeneous catalysis will play a key role to secure the supply of energy, chemicals and fuels in the future. Methane is the main constituent of natural gas and biogas and it is also found in crystalline hydrates at the continental slopes of many oceans and in permafrost areas. In view of this vast reserves and resources, the use of methane as chemical feedstock has to be intensified. The present review presents recent results and developments in heterogeneous catalytic methane conversion to synthesis gas, hydrogen cyanide, ethylene, methanol, formaldehyde, methyl chloride, methyl bromide and aromatics. After presenting recent estimates of methane reserves and resources the physico-chemical challenges of methane activation are discussed. Subsequent to this recent results in methane conversion to synthesis gas by steam reforming, dry reforming, autothermal reforming and catalytic partial oxidation are presented. The high temperature methane conversion to hydrogen cyanide via the BMA-process and the Andrussow-process is considered as well. The second part of this review focuses on one-step conversion of methane into chemicals. This includes the oxidative coupling of methane to ethylene mediated by oxygen and sulfur, the direct oxidation of methane to formaldehyde and methanol, the halogenation and oxy-halogenation of methane to methyl chloride and methyl bromide and finally the non-oxidative methane aromatization to benzene and related aromates. Opportunities and limits of the various activation strategies are discussed. .

478 citations


Journal ArticleDOI
TL;DR: A cobalt protoporphyrin immobilized on a pyrolytic graphite electrode that reduces carbon dioxide in an aqueous acidic solution at relatively low overpotential, with an efficiency and selectivity comparable to the best porphyrIn-based electrocatalyst in the literature.
Abstract: The electrochemical conversion of carbon dioxide and water into useful products is a major challenge in facilitating a closed carbon cycle. Here we report a cobalt protoporphyrin immobilized on a pyrolytic graphite electrode that reduces carbon dioxide in an aqueous acidic solution at relatively low overpotential (0.5 V), with an efficiency and selectivity comparable to the best porphyrin-based electrocatalyst in the literature. While carbon monoxide is the main reduction product, we also observe methane as by-product. The results of our detailed pH-dependent studies are explained consistently by a mechanism in which carbon dioxide is activated by the cobalt protoporphyrin through the stabilization of a radical intermediate, which acts as Bronsted base. The basic character of this intermediate explains how the carbon dioxide reduction circumvents a concerted proton–electron transfer mechanism, in contrast to hydrogen evolution. Our results and their mechanistic interpretations suggest strategies for designing improved catalysts.

428 citations


Journal ArticleDOI
TL;DR: The potential for methanotrophs and their consortia to generate value while using methane as a carbon source is demonstrated.
Abstract: Methane is an abundant gas used in energy recovery systems, heating, and transport. Methanotrophs are bacteria capable of using methane as their sole carbon source. Although intensively researched, the myriad of potential biotechnological applications of methanotrophic bacteria has not been comprehensively discussed in a single review. Methanotrophs can generate single-cell protein, biopolymers, components for nanotechnology applications (surface layers), soluble metabolites (methanol, formaldehyde, organic acids, and ectoine), lipids (biodiesel and health supplements), growth media, and vitamin B12 using methane as their carbon source. They may be genetically engineered to produce new compounds such as carotenoids or farnesene. Some enzymes (dehydrogenases, oxidase, and catalase) are valuable products with high conversion efficiencies and can generate methanol or sequester CO2 as formic acid ex vivo. Live cultures can be used for bioremediation, chemical transformation (propene to propylene oxide), wastewater denitrification, as components of biosensors, or possibly for directly generating electricity. This review demonstrates the potential for methanotrophs and their consortia to generate value while using methane as a carbon source. While there are notable challenges using a low solubility gas as a carbon source, the massive methane resource, and the potential cost savings while sequestering a greenhouse gas, keeps interest piqued in these unique bacteria.

342 citations


Journal ArticleDOI
TL;DR: In this article, both experimental and chemical kinetic model-predicted ignition delay time data are provided covering a range of conditions relevant to gas turbine environments (T = 600-1600 K, p = 7-41 K, ϕ ǫ = 0.3, 0.5, 1.0, and 2.0 in ‘air’ mixtures).

342 citations


Journal ArticleDOI
TL;DR: In this article, the authors report dissolved carbon dioxide, methane and nitrous oxide concentrations from 12 rivers in sub-Saharan Africa, including seasonally resolved sampling at 39 sites, acquired between 2006 and 2014.
Abstract: Carbon dioxide emissions to the atmosphere from inland waters—streams, rivers, lakes and reservoirs—are nearly equivalent to ocean and land sinks globally. Inland waters can be an important source of methane and nitrous oxide emissions as well, but emissions are poorly quantified, especially in Africa. Here we report dissolved carbon dioxide, methane and nitrous oxide concentrations from 12 rivers in sub-Saharan Africa, including seasonally resolved sampling at 39 sites, acquired between 2006 and 2014. Fluxes were calculated from published gas transfer velocities, and upscaled to the area of all sub-Saharan African rivers using available spatial data sets. Carbon dioxide-equivalent emissions from river channels alone were about 0.4 Pg carbon per year, equivalent to two-thirds of the overall net carbon land sink previously reported for Africa. Including emissions from wetlands of the Congo river increases the total carbon dioxide-equivalent greenhouse-gas emissions to about 0.9 Pg carbon per year, equivalent to about one quarter of the global ocean and terrestrial combined carbon sink. Riverine carbon dioxide and methane emissions increase with wetland extent and upland biomass. We therefore suggest that future changes in wetland and upland cover could strongly affect greenhouse-gas emissions from African inland waters. Inland waters are important sources of greenhouse gases. Measurements over eight years suggest that African inland waters are a substantial source of greenhouse gases, equivalent to a quarter of the global land and ocean carbon sink.

330 citations


Journal ArticleDOI
TL;DR: Co-digestion of OFMSW and biological sludge and Gompertz model determine productivities and kinetics within the 7th day of experiment give an indication of maximum methane productivity.

327 citations


Journal ArticleDOI
TL;DR: In this paper, the authors investigated the gas production from methane hydrate-bearing sediments, and compared the three methods: depressurization, two-cycle warm-water injection and a combination of the two methods.

314 citations


Journal ArticleDOI
TL;DR: A discussion on the different materials used to produce membranes for gas separation is given in this paper, including inorganic, organic and mixed matrix membranes, as well as polymer of intrinsic microporosity (PIM).
Abstract: Biogas is a renewable energy source like solar and wind energies and mostly produced from anaerobic digestion (AD). The production of biogas is a well-established technology, but its commercial utilization is limited because on-site purification is needed before its transport or use. Biogas composition varies with the biomass digested and contains mainly methane (CH4) and carbon dioxide (CO2), as well as traces of hydrogen sulfide (H2S), ammonia (NH3), hydrogen (H2), nitrogen (N2), carbon monoxide (CO), oxygen (O2). In some cases dust particles and siloxanes are present. Several purification processes including pressurized water scrubbing, amine swing absorption, pressure swing adsorption, temperature swing adsorption, cryogenic separation and membrane technologies have been developed. Nevertheless, membrane technology is a relatively recent but very promising technology. Also, hybrid processes where membranes are combined with other processes are believed to have lower investment and operation costs compared with other processes. In this report, a discussion on the different materials used to produce membranes for gas separation is given including inorganic, organic and mixed matrix membranes, as well as polymer of intrinsic microporosity (PIM). Advantages and limitations for each type are discussed and comparisons are made in terms of permeability and diffusivity for a range of operating conditions.

Journal ArticleDOI
TL;DR: In this article, Ceria supported Ni, Co monometallic and Ni-Co bimetallic catalysts were prepared by incipient wetness impregnation method, calcined at two different temperatures (700°C and 900°C) and tested for dry reforming of methane reaction at 700°C.
Abstract: Ceria supported Ni, Co monometallic and Ni–Co bimetallic catalysts were prepared by incipient wetness impregnation method, calcined at two different temperatures (700 °C and 900 °C) and tested for dry reforming of methane reaction at 700 °C. The activities of ceria-based Ni containing catalysts decreased with increasing calcination temperature accompanied by a decrease in coke deposition. While Ni/CeO 2 and Ni–Co/CeO 2 catalysts exhibited comparable high activities, Co/CeO 2 catalysts exhibited very low activity. The lower activity of Co/CeO 2 catalyst was attributed to strong metal support interaction (SMSI). The SMSI effect was confirmed with TEM images showing a layer of support coating the metal particles. The diversity of the deposited carbon structures in terms morphology (straight long filaments, highly entangled and curly shaped filaments, filaments with knuckle-like structure and carbon onions) was noted. In addition to the carbon buildup, the deactivation was observed to be due to the loss of active metals in the carbon filaments.

Journal ArticleDOI
TL;DR: In this article, the authors investigated the role of the sensible heat of the reservoir and ambient heat transfer in hydrate dissociation in natural gas hydrate reformation and ice generation.

Journal ArticleDOI
TL;DR: An overview of the most recent advances pertaining to metabolic engineering of microbial methane utilization is presented and some ideas concerning metabolic improvements for production of acetyl-CoA and pyruvate, two main precursors for bioconversion, are presented.

Journal ArticleDOI
TL;DR: Theoretical estimates of the methane yields resulting from the anaerobic digestion of the liquid by-products are presented and optimal reaction conditions to maximise these identified.

Journal ArticleDOI
TL;DR: In this paper, a review studying all development in laboratory-scale research on TCD, especially the recent advances like co-feeding effect and catalyst regeneration for augmenting the productivity of the whole process is presented.
Abstract: Thermocatalytic decomposition of methane (TCD) is a fully green single step technology for producing hydrogen and nano-carbon. This review studying all development in laboratory-scale research on TCD, especially the recent advances like co-feeding effect and catalyst regeneration for augmenting the productivity of the whole process. Although a great success on the laboratory-scale has been fulfilled, TCD for greenhouse gas (GHG) free hydrogen production is still in its infancy. The need for commercialization of TCD is greater than ever in the present situation of huge GHG emission. TCD usually examined over various kind of catalysts, such as monometallic, bimetallic, trimetallic, combination of metal–metal oxide, carbonaceous and/or metal doped carbon catalysts. Deactivation of catalysts is the prime drawback found in TCD process. Catalyst regeneration and co-feeding of methane with other hydrocarbon are the two solutions put forwarded in accordance to overcome deactivation hurdle. Higher amount of co-feed hydrocarbon in situ produce more amount of highly active carbonaceous deposits which assist further methane decomposition to produce additional hydrogen to a great extent. The methane conversion rate increases with increase in the temperature and decreases with the flow rate in the co-feeding process in a similar manner as observed in normal TCD. The presence of co-components in the post-reaction stream is a key challenge tackled in the co-feeding and regeneration. Hence, this review hypothesizing the integration of hydrogen separation membrane in to methane decomposition reactor for online hydrogen separation.

Journal ArticleDOI
TL;DR: In this article, the experimental biochemical methane potentials (BMP) of typical food waste (FW) and straw from northern China were individually measured in a 1L enclosed reactor at 35°C, and were 0.26 and 0.16m 3 /kg-VS (volatile solids), respectively.

Journal ArticleDOI
TL;DR: This study quantifies the full seasonal cycle of methane emissions and the fractional contribution of natural gas for the urbanized region centered on Boston and suggests that natural-gas–consuming regions may be larger sources of methane to the atmosphere than is currently estimated and represent areas of significant resource loss.
Abstract: Methane emissions from natural gas delivery and end use must be quantified to evaluate the environmental impacts of natural gas and to develop and assess the efficacy of emission reduction strategies. We report natural gas emission rates for 1 y in the urban region of Boston, using a comprehensive atmospheric measurement and modeling framework. Continuous methane observations from four stations are combined with a high-resolution transport model to quantify the regional average emission flux, 18.5 ± 3.7 (95% confidence interval) g CH4⋅m−2⋅y−1. Simultaneous observations of atmospheric ethane, compared with the ethane-to-methane ratio in the pipeline gas delivered to the region, demonstrate that natural gas accounted for ∼60–100% of methane emissions, depending on season. Using government statistics and geospatial data on natural gas use, we find the average fractional loss rate to the atmosphere from all downstream components of the natural gas system, including transmission, distribution, and end use, was 2.7 ± 0.6% in the Boston urban region, with little seasonal variability. This fraction is notably higher than the 1.1% implied by the most closely comparable emission inventory.

Journal ArticleDOI
TL;DR: In this paper, the authors examined the various catalytic systems being evaluated for the dry reforming of methane with emphasis on operating parameters, activity, and coke deposition and highlighted the benefits of utilizing methane from natural gas and other sources, where carbon dioxide is considered as an impurity component.
Abstract: Summary The dry (CO2) reforming of methane is a great promising technology, particularly because of its dual advantages of natural gas valorization and mitigating global warming via carbon dioxide sequestration. However, coke management is the most difficult problem in commercialization of the process. We have therefore examined in this paper the various catalytic systems being evaluated for the dry reforming with emphasis on operating parameters, activity, and coke deposition. Other factors such as the catalyst promoter, the reactor system, and the periodical regeneration were also critically reviewed. The benefits of utilizing methane from natural gas and other sources, where carbon dioxide is considered as an impurity component, are emphasized. Structured basic catalysts, with periodic regeneration certainties, are strong candidates for industrial applications. Therefore, efforts to build commercial scales for the benefit of global energy industries were highlighted. Copyright © 2015 John Wiley & Sons, Ltd.

Posted Content
TL;DR: In this article, a review studying all development in laboratory-scale research on thermocatalytic decomposition of methane (TCD), especially the recent advances like co-feeding effect and catalyst regeneration for augmenting the productivity of the whole process is presented.
Abstract: Thermocatalytic decomposition of methane (TCD) is a fully green single step technology for producing hydrogen and nano-carbon This review studying all development in laboratory-scale research on TCD, especially the recent advances like co-feeding effect and catalyst regeneration for augmenting the productivity of the whole process Although a great success on the laboratory-scale has been fulfilled, TCD for greenhouse gas (GHG) free hydrogen production is still in its infancy The need for commercialization of TCD is greater than ever in the present situation of huge GHG emission TCD usually examined over various kind of catalysts, such as monometallic, bimetallic, trimetallic, combination of metal-metal oxide, carbonaceous and/or metal doped carbon catalysts Deactivation of catalysts is the prime drawback found in TCD process Catalyst regeneration and co-feeding of methane with other hydrocarbon are the two solutions put forwarded in accordance to overcome deactivation hurdle Higher amount of co-feed hydrocarbon in situ produce more amount of highly active carbonaceous deposits which assist further methane decomposition to produce additional hydrogen to a great extent The methane conversion rate increases with increase in the temperature and decreases with the flow rate in the co-feeding process in a similar manner as observed in normal TCD The presence of co-components in the post-reaction stream is a key challenge tackled in the co-feeding and regeneration Hence, this review hypothesizing the integration of hydrogen separation membrane in to methane decomposition reactor for online hydrogen separation

Journal ArticleDOI
TL;DR: It is shown that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM, the first field evidence for iron- dependent AOM in brackish coastal surface sediments and Laboratory incubation studies of these sediments suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction.
Abstract: Methane is a powerful greenhouse gas and its biological conversion in marine sediments, largely controlled by anaerobic oxidation of methane (AOM), is a crucial part of the global carbon cycle. However, little is known about the role of iron oxides as an oxidant for AOM. Here we provide the first field evidence for iron-dependent AOM in brackish coastal surface sediments and show that methane produced in Bothnian Sea sediments is oxidized in distinct zones of iron- and sulfate-dependent AOM. At our study site, anthropogenic eutrophication over recent decades has led to an upward migration of the sulfate/methane transition zone in the sediment. Abundant iron oxides and high dissolved ferrous iron indicate iron reduction in the methanogenic sediments below the newly established sulfate/methane transition. Laboratory incubation studies of these sediments strongly suggest that the in situ microbial community is capable of linking methane oxidation to iron oxide reduction. Eutrophication of coastal environments may therefore create geochemical conditions favorable for iron-mediated AOM and thus increase the relevance of iron-dependent methane oxidation in the future. Besides its role in mitigating methane emissions, iron-dependent AOM strongly impacts sedimentary iron cycling and related biogeochemical processes through the reduction of large quantities of iron oxides.

Journal ArticleDOI
TL;DR: The results indicate that the seep microbiome is structured according to metacommunity processes and that few cosmopolitan microbial taxa mediate the bulk of methane oxidation, with global relevance to methane emission in the ocean.
Abstract: Methane seeps are widespread seafloor ecosystems shaped by the emission of gas from seabed reservoirs. The microorganisms inhabiting methane seeps transform the chemical energy in methane to products that sustain rich benthic communities around the gas leaks. Despite the biogeochemical relevance of microbial methane removal at seeps, the global diversity and dispersion of seep microbiota remain unknown. Here we determined the microbial diversity and community structure of 23 globally distributed methane seeps and compared these to the microbial communities of 54 other seafloor ecosystems, including sulfate–methane transition zones, hydrothermal vents, coastal sediments, and deep-sea surface and subsurface sediments. We found that methane seep communities show moderate levels of microbial richness compared with other seafloor ecosystems and harbor distinct bacterial and archaeal taxa with cosmopolitan distribution and key biogeochemical functions. The high relative sequence abundance of ANME (anaerobic methanotrophic archaea), as well as aerobic Methylococcales, sulfate-reducing Desulfobacterales, and sulfide-oxidizing Thiotrichales, matches the most favorable microbial metabolisms at methane seeps in terms of substrate supply and distinguishes the seep microbiome from other seafloor microbiomes. The key functional taxa varied in relative sequence abundance between different seeps due to the environmental factors, sediment depth and seafloor temperature. The degree of endemism of the methane seep microbiome suggests a high local diversification in these heterogeneous but long-lived ecosystems. Our results indicate that the seep microbiome is structured according to metacommunity processes and that few cosmopolitan microbial taxa mediate the bulk of methane oxidation, with global relevance to methane emission in the ocean.

Journal ArticleDOI
TL;DR: It is reported that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale.
Abstract: It is crucial to develop a catalyst made of earth-abundant elements highly active for a complete oxidation of methane at a relatively low temperature NiCo2O4 consisting of earth-abundant elements which can completely oxidize methane in the temperature range of 350-550 °C Being a cost-effective catalyst, NiCo2O4 exhibits activity higher than precious-metal-based catalysts Here we report that the higher catalytic activity at the relatively low temperature results from the integration of nickel cations, cobalt cations and surface lattice oxygen atoms/oxygen vacancies at the atomic scale In situ studies of complete oxidation of methane on NiCo2O4 and theoretical simulations show that methane dissociates to methyl on nickel cations and then couple with surface lattice oxygen atoms to form -CH3O with a following dehydrogenation to -CH2O; a following oxidative dehydrogenation forms CHO; CHO is transformed to product molecules through two different sub-pathways including dehydrogenation of OCHO and CO oxidation

Journal ArticleDOI
TL;DR: This work reconciles top-down and bottom-up methane emissions estimates in one of the country’s major natural gas production basins using easily replicable measurement and data integration techniques and reduces uncertainty in top- down estimates by using repeated mass balance measurements, as well as ethane as a fingerprint for source attribution.
Abstract: Published estimates of methane emissions from atmospheric data (top-down approaches) exceed those from source-based inventories (bottom-up approaches), leading to conflicting claims about the climate implications of fuel switching from coal or petroleum to natural gas. Based on data from a coordinated campaign in the Barnett Shale oil and gas-producing region of Texas, we find that top-down and bottom-up estimates of both total and fossil methane emissions agree within statistical confidence intervals (relative differences are 10% for fossil methane and 0.1% for total methane). We reduced uncertainty in top-down estimates by using repeated mass balance measurements, as well as ethane as a fingerprint for source attribution. Similarly, our bottom-up estimate incorporates a more complete count of facilities than past inventories, which omitted a significant number of major sources, and more effectively accounts for the influence of large emission sources using a statistical estimator that integrates observations from multiple ground-based measurement datasets. Two percent of oil and gas facilities in the Barnett accounts for half of methane emissions at any given time, and high-emitting facilities appear to be spatiotemporally variable. Measured oil and gas methane emissions are 90% larger than estimates based on the US Environmental Protection Agency’s Greenhouse Gas Inventory and correspond to 1.5% of natural gas production. This rate of methane loss increases the 20-y climate impacts of natural gas consumed in the region by roughly 50%.

Journal ArticleDOI
19 Feb 2015-Nature
TL;DR: Banerjee et al. as discussed by the authors reported the core structures of compound Q and the following product complex, compound T, using time-resolved resonance Raman spectroscopy (TR3) for short-lived species.
Abstract: Time-resolved resonance Raman vibrational spectroscopy was used to study the mechanism of soluble methane monooxygenase and obtain structural information on the key reaction cycle intermediate, compound Q, which contains a unique dinuclear FeIV cluster that breaks the strong C-H bond of methane and inserts an oxygen atom (from O2) to form methanol Using time-resolved resonance Raman vibrational spectroscopy, Rahul Banerjee et al have determined the structure of 'compound Q', a key transient intermediate from the soluble methane monooxygenase (sMMO) system found in methanotrophic bacteria Q is the strongest known biological oxidant and catalyses cleavage of the ultimately stable C–H bond of methane with insertion of oxygen to form the liquid fuel methanol With a better understanding of the structure and mechanism of action of Q it might be possible to synthesize small molecule enzyme mimetics that could convert naturally occurring methane to methanol, thereby converting a damaging greenhouse gas into a potentially important source of liquid fuel and chemicals Methane monooxygenase (MMO) catalyses the O2-dependent conversion of methane to methanol in methanotrophic bacteria, thereby preventing the atmospheric egress of approximately one billion tons of this potent greenhouse gas annually The key reaction cycle intermediate of the soluble form of MMO (sMMO) is termed compound Q (Q) Q contains a unique dinuclear FeIV cluster that reacts with methane to break an exceptionally strong 105 kcal mol−1 C-H bond and insert one oxygen atom1,2 No other biological oxidant, except that found in the particulate form of MMO, is capable of such catalysis The structure of Q remains controversial despite numerous spectroscopic, computational and synthetic model studies2,3,4,5,6,7 A definitive structural assignment can be made from resonance Raman vibrational spectroscopy but, despite efforts over the past two decades, no vibrational spectrum of Q has yet been obtained Here we report the core structures of Q and the following product complex, compound T, using time-resolved resonance Raman spectroscopy (TR3) TR3 permits fingerprinting of intermediates by their unique vibrational signatures through extended signal averaging for short-lived species We report unambiguous evidence that Q possesses a bis-μ-oxo diamond core structure and show that both bridging oxygens originate from O2 This observation strongly supports a homolytic mechanism for O-O bond cleavage We also show that T retains a single oxygen atom from O2 as a bridging ligand, while the other oxygen atom is incorporated into the product8 Capture of the extreme oxidizing potential of Q is of great contemporary interest for bioremediation and the development of synthetic approaches to methane-based alternative fuels and chemical industry feedstocks Insight into the formation and reactivity of Q from the structure reported here is an important step towards harnessing this potential

Journal ArticleDOI
TL;DR: This communication reports the discovery of several small-pore Cu-zeolites and zeotypes that produce methanol from methane and water vapor, and produce more meethanol per copper atom than Cu-ZSM-5 and Cu-mordenite.

Journal ArticleDOI
TL;DR: In this paper, a linear combination approach has been developed to predict the Langmuir capacity of shales based on the mass fractions of their organic and inorganic components, which can be used to estimate the in situ sorption capacity of shale layers as a function of burial depth (formation pressure and temperature), and composition.

Journal ArticleDOI
TL;DR: In this paper, absorption lines from water, methane, and carbon monoxide are detected in the atmosphere of exoplanet HR 8799 b. The majority of the lines are produced by CO and H2O, but several lines clearly belong to CH4.
Abstract: Absorption lines from water, methane, and carbon monoxide are detected in the atmosphere of exoplanet HR 8799 b. A medium-resolution spectrum presented here shows well-resolved and easily identified spectral features from all three molecules across the K band. The majority of the lines are produced by CO and H2O, but several lines clearly belong to CH4. Comparisons between these data and atmosphere models covering a range of temperatures and gravities yield log mole fractions of H2O between −3.09 and −3.91, CO between −3.30 and −3.72, and CH4 between −5.06 and −5.85. More precise mole fractions are obtained for each temperature and gravity studied. A reanalysis of H-band data, previously obtained at a similar spectral resolution, results in a nearly identical water abundance as determined from the K-band spectrum. The methane abundance is shown to be sensitive to vertical mixing and indicates an eddy diffusion coefficient in the range of 106–108 cm2 s−1, comparable to mixing in the deep troposphere of Jupiter. The model comparisons also indicate a carbon-to-oxygen ratio (C/O) between ~0.58 and 0.7, encompassing previous estimates for a second planet in the same system, HR 8799 c. Super-stellar C/O could indicate planet formation by core-accretion; however, the range of possible C/O for these planets (and the star) is currently too large to comment strongly on planet formation. More precise values of the bulk properties (e.g., effective temperature and surface gravity) are needed for improved abundance estimates.

Journal ArticleDOI
TL;DR: The United States Congress enacted the Methane Hydrate Research and Development Act of 2000 and the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough as mentioned in this paper.
Abstract: Recognizing the importance of methane hydrate research and the need for a coordinated effort, the United States Congress enacted the Methane Hydrate Research and Development Act of 2000. At the same time, the Ministry of International Trade and Industry in Japan launched a research program to develop plans for a methane hydrate exploratory drilling project in the Nankai Trough. India, China, the Republic of Korea, and other nations also have established large methane hydrate research and development programs. Government-funded scientific research drilling expeditions and production test studies have provided a wealth of information on the occurrence of methane hydrates in nature. Numerous studies have shown that the amount of gas stored as methane hydrates in the world may exceed the volume of known organic carbon sources. However, methane hydrates represent both a scientific and technical challenge, and much remains to be learned about their characteristics and occurrence in nature. Methane hydrate resea...

Journal ArticleDOI
TL;DR: These findings challenge precepts surrounding wetland carbon cycling and demonstrate the environmental relevance of an anaerobic methane sink in ecosystems traditionally considered strong methane sources.
Abstract: Freshwater wetlands are among the largest natural sources of methane to the atmosphere. Here, the authors report rates of anaerobic methane oxidation which rival those in marine environments, highlighting the importance of a long-overlooked anaerobic methane sink.