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Showing papers on "Methane published in 2016"


Journal ArticleDOI
Marielle Saunois1, Philippe Bousquet1, Ben Poulter2, Anna Peregon1, Philippe Ciais1, Josep G. Canadell3, Edward J. Dlugokencky4, Giuseppe Etiope5, David Bastviken6, Sander Houweling7, Greet Janssens-Maenhout, Francesco N. Tubiello8, Simona Castaldi, Robert B. Jackson9, Mihai Alexe, Vivek K. Arora, David J. Beerling10, Peter Bergamaschi, Donald R. Blake11, Gordon Brailsford12, Victor Brovkin13, Lori Bruhwiler4, Cyril Crevoisier14, Patrick M. Crill, Kristofer R. Covey15, Charles L. Curry16, Christian Frankenberg17, Nicola Gedney18, Lena Höglund-Isaksson19, Misa Ishizawa20, Akihiko Ito20, Fortunat Joos21, Heon Sook Kim20, Thomas Kleinen13, Paul B. Krummel3, Jean-Francois Lamarque22, Ray L. Langenfelds3, Robin Locatelli1, Toshinobu Machida20, Shamil Maksyutov20, Kyle C. McDonald23, Julia Marshall13, Joe R. Melton, Isamu Morino18, Vaishali Naik24, Simon O'Doherty25, Frans-Jan W. Parmentier26, Prabir K. Patra27, Changhui Peng28, Shushi Peng1, Glen P. Peters29, Isabelle Pison1, Catherine Prigent30, Ronald G. Prinn31, Michel Ramonet1, William J. Riley32, Makoto Saito20, Monia Santini, Ronny Schroeder23, Ronny Schroeder33, Isobel J. Simpson11, Renato Spahni21, P. Steele3, Atsushi Takizawa34, Brett F. Thornton, Hanqin Tian35, Yasunori Tohjima20, Nicolas Viovy1, Apostolos Voulgarakis36, Michiel van Weele37, Guido R. van der Werf38, Ray F. Weiss39, Christine Wiedinmyer22, David J. Wilton10, Andy Wiltshire18, Doug Worthy40, Debra Wunch41, Xiyan Xu32, Yukio Yoshida20, Bowen Zhang35, Zhen Zhang2, Qiuan Zhu42 
TL;DR: The Global Carbon Project (GCP) as discussed by the authors is a consortium of multi-disciplinary scientists, including atmospheric physicists and chemists, biogeochemists of surface and marine emissions, and socio-economists who study anthropogenic emissions.
Abstract: . The global methane (CH4) budget is becoming an increasingly important component for managing realistic pathways to mitigate climate change. This relevance, due to a shorter atmospheric lifetime and a stronger warming potential than carbon dioxide, is challenged by the still unexplained changes of atmospheric CH4 over the past decade. Emissions and concentrations of CH4 are continuing to increase, making CH4 the second most important human-induced greenhouse gas after carbon dioxide. Two major difficulties in reducing uncertainties come from the large variety of diffusive CH4 sources that overlap geographically, and from the destruction of CH4 by the very short-lived hydroxyl radical (OH). To address these difficulties, we have established a consortium of multi-disciplinary scientists under the umbrella of the Global Carbon Project to synthesize and stimulate research on the methane cycle, and producing regular (∼ biennial) updates of the global methane budget. This consortium includes atmospheric physicists and chemists, biogeochemists of surface and marine emissions, and socio-economists who study anthropogenic emissions. Following Kirschke et al. (2013), we propose here the first version of a living review paper that integrates results of top-down studies (exploiting atmospheric observations within an atmospheric inverse-modelling framework) and bottom-up models, inventories and data-driven approaches (including process-based models for estimating land surface emissions and atmospheric chemistry, and inventories for anthropogenic emissions, data-driven extrapolations). For the 2003–2012 decade, global methane emissions are estimated by top-down inversions at 558 Tg CH4 yr−1, range 540–568. About 60 % of global emissions are anthropogenic (range 50–65 %). Since 2010, the bottom-up global emission inventories have been closer to methane emissions in the most carbon-intensive Representative Concentrations Pathway (RCP8.5) and higher than all other RCP scenarios. Bottom-up approaches suggest larger global emissions (736 Tg CH4 yr−1, range 596–884) mostly because of larger natural emissions from individual sources such as inland waters, natural wetlands and geological sources. Considering the atmospheric constraints on the top-down budget, it is likely that some of the individual emissions reported by the bottom-up approaches are overestimated, leading to too large global emissions. Latitudinal data from top-down emissions indicate a predominance of tropical emissions (∼ 64 % of the global budget, The most important source of uncertainty on the methane budget is attributable to emissions from wetland and other inland waters. We show that the wetland extent could contribute 30–40 % on the estimated range for wetland emissions. Other priorities for improving the methane budget include the following: (i) the development of process-based models for inland-water emissions, (ii) the intensification of methane observations at local scale (flux measurements) to constrain bottom-up land surface models, and at regional scale (surface networks and satellites) to constrain top-down inversions, (iii) improvements in the estimation of atmospheric loss by OH, and (iv) improvements of the transport models integrated in top-down inversions. The data presented here can be downloaded from the Carbon Dioxide Information Analysis Center ( http://doi.org/10.3334/CDIAC/GLOBAL_METHANE_BUDGET_2016_V1.1 ) and the Global Carbon Project.

771 citations


Journal ArticleDOI
06 Oct 2016-Nature
TL;DR: Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syng as into lower olefins.
Abstract: Lower olefins-generally referring to ethylene, propylene and butylene-are basic carbon-based building blocks that are widely used in the chemical industry, and are traditionally produced through thermal or catalytic cracking of a range of hydrocarbon feedstocks, such as naphtha, gas oil, condensates and light alkanes. With the rapid depletion of the limited petroleum reserves that serve as the source of these hydrocarbons, there is an urgent need for processes that can produce lower olefins from alternative feedstocks. The 'Fischer-Tropsch to olefins' (FTO) process has long offered a way of producing lower olefins directly from syngas-a mixture of hydrogen and carbon monoxide that is readily derived from coal, biomass and natural gas. But the hydrocarbons obtained with the FTO process typically follow the so-called Anderson-Schulz-Flory distribution, which is characterized by a maximum C2-C4 hydrocarbon fraction of about 56.7 per cent and an undesired methane fraction of about 29.2 per cent (refs 1, 10, 11, 12). Here we show that, under mild reaction conditions, cobalt carbide quadrangular nanoprisms catalyse the FTO conversion of syngas with high selectivity for the production of lower olefins (constituting around 60.8 per cent of the carbon products), while generating little methane (about 5.0 per cent), with the ratio of desired unsaturated hydrocarbons to less valuable saturated hydrocarbons amongst the C2-C4 products being as high as 30. Detailed catalyst characterization during the initial reaction stage and theoretical calculations indicate that preferentially exposed {101} and {020} facets play a pivotal role during syngas conversion, in that they favour olefin production and inhibit methane formation, and thereby render cobalt carbide nanoprisms a promising new catalyst system for directly converting syngas into lower olefins.

578 citations



Journal ArticleDOI
TL;DR: In this paper, the authors presented new calculations of the radiative forcing (RF) for the three main well-mixed greenhouse gases, methane, nitrous oxide, and carbon dioxide.
Abstract: New calculations of the radiative forcing (RF) are presented for the three main well‐mixed greenhouse gases, methane, nitrous oxide, and carbon dioxide. Methane’s RF is particularly impacted because of the inclusion of the shortwave forcing; the 1750–2011 RF is about 25% higher (increasing from 0.48 W m−2 to 0.61 W m−2) compared to the value in the Intergovernmental Panel on Climate Change (IPCC) 2013 assessment; the 100 year global warming potential is 14% higher than the IPCC value. We present new simplified expressions to calculate RF. Unlike previous expressions used by IPCC, the new ones include the overlap between CO2 and N2O; for N2O forcing, the CO2 overlap can be as important as the CH4 overlap. The 1750–2011 CO2 RF is within 1% of IPCC’s value but is about 10% higher when CO2 amounts reach 2000 ppm, a value projected to be possible under the extended RCP8.5 scenario.

484 citations


Journal ArticleDOI
TL;DR: This study identifies archaea of the order Methanosarcinales, related to “Candidatus Methanoperedens nitroreducens,” which couple the reduction of environmentally relevant particulate forms of iron and manganese to methane oxidation, filling one of the remaining lacunas in anaerobic methane oxidation.
Abstract: Anaerobic oxidation of methane (AOM) is crucial for controlling the emission of this potent greenhouse gas to the atmosphere. Nitrite-, nitrate-, and sulfate-dependent methane oxidation is well-documented, but AOM coupled to the reduction of oxidized metals has so far been demonstrated only in environmental samples. Here, using a freshwater enrichment culture, we show that archaea of the order Methanosarcinales, related to “Candidatus Methanoperedens nitroreducens,” couple the reduction of environmentally relevant forms of Fe^(3+) and Mn^(4+) to the oxidation of methane. We obtained an enrichment culture of these archaea under anaerobic, nitrate-reducing conditions with a continuous supply of methane. Via batch incubations using [^(13)C]methane, we demonstrated that soluble ferric iron (Fe^(3+), as Fe-citrate) and nanoparticulate forms of Fe^(3+) and Mn^(4+) supported methane-oxidizing activity. CO_2 and ferrous iron (Fe^(2+)) were produced in stoichiometric amounts. Our study connects the previous finding of iron-dependent AOM to microorganisms detected in numerous habitats worldwide. Consequently, it enables a better understanding of the interaction between the biogeochemical cycles of iron and methane.

445 citations


Journal ArticleDOI
21 Apr 2016-Nature
TL;DR: Negative gas adsorption extends the series of counterintuitive phenomena such as negative thermal expansion and negative refractive indices and may be interpreted as an adsorptive analogue of force-amplifying negative compressibility transitions proposed for metamaterials.
Abstract: Adsorption-based phenomena are important in gas separations, such as the treatment of greenhouse-gas and toxic-gas pollutants, and in water-adsorption-based heat pumps for solar cooling systems. The ability to tune the pore size, shape and functionality of crystalline porous coordination polymers--or metal-organic frameworks (MOFs)--has made them attractive materials for such adsorption-based applications. The flexibility and guest-molecule-dependent response of MOFs give rise to unexpected and often desirable adsorption phenomena. Common to all isothermal gas adsorption phenomena, however, is increased gas uptake with increased pressure. Here we report adsorption transitions in the isotherms of a MOF (DUT-49) that exhibits a negative gas adsorption; that is, spontaneous desorption of gas (methane and n-butane) occurs during pressure increase in a defined temperature and pressure range. A combination of in situ powder X-ray diffraction, gas adsorption experiments and simulations shows that this adsorption behaviour is controlled by a sudden hysteretic structural deformation and pore contraction of the MOF, which releases guest molecules. These findings may enable technologies using frameworks capable of negative gas adsorption for pressure amplification in micro- and macroscopic system engineering. Negative gas adsorption extends the series of counterintuitive phenomena such as negative thermal expansion and negative refractive indices and may be interpreted as an adsorptive analogue of force-amplifying negative compressibility transitions proposed for metamaterials.

437 citations


Journal ArticleDOI
10 Mar 2016-Nature
TL;DR: The cumulative warming capacity of concurrent biogenic methane and nitrous oxide emissions is a factor of about two larger than the cooling effect resulting from the global land carbon dioxide uptake from 2001 to 2010, which results in a net positive cumulative impact of the three greenhouse gases on the planetary energy budget.
Abstract: The net balance of terrestrial biogenic greenhouse gases produced as a result of human activities and the climatic impact of this balance are uncertain; here the net cumulative impact of the three greenhouse gases, methane, nitrous oxide and carbon dioxide, on the planetary energy budget from 2001 to 2010 is a warming of the planet. The biogenic fluxes of individual greenhouse gases have extensively studied, but the net terrestrial biogenic greenhouse gas balance as a result of human activities and its climatic impact remains uncertain. Hanqin Tian et al. have quantified the net cumulative impact of three greenhouse gases — methane, nitrous oxide and carbon dioxide — on the planetary energy budget. From 2001 to 2010, they find a net positive (warming) cumulative impact and conclude that a reduction in agricultural methane and nitrous oxide emissions — in particular in Southern Asia — may help mitigate climate change. The terrestrial biosphere can release or absorb the greenhouse gases, carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O), and therefore has an important role in regulating atmospheric composition and climate1. Anthropogenic activities such as land-use change, agriculture and waste management have altered terrestrial biogenic greenhouse gas fluxes, and the resulting increases in methane and nitrous oxide emissions in particular can contribute to climate change2,3. The terrestrial biogenic fluxes of individual greenhouse gases have been studied extensively4,5,6, but the net biogenic greenhouse gas balance resulting from anthropogenic activities and its effect on the climate system remains uncertain. Here we use bottom-up (inventory, statistical extrapolation of local flux measurements, and process-based modelling) and top-down (atmospheric inversions) approaches to quantify the global net biogenic greenhouse gas balance between 1981 and 2010 resulting from anthropogenic activities and its effect on the climate system. We find that the cumulative warming capacity of concurrent biogenic methane and nitrous oxide emissions is a factor of about two larger than the cooling effect resulting from the global land carbon dioxide uptake from 2001 to 2010. This results in a net positive cumulative impact of the three greenhouse gases on the planetary energy budget, with a best estimate (in petagrams of CO2 equivalent per year) of 3.9 ± 3.8 (top down) and 5.4 ± 4.8 (bottom up) based on the GWP100 metric (global warming potential on a 100-year time horizon). Our findings suggest that a reduction in agricultural methane and nitrous oxide emissions, particularly in Southern Asia, may help mitigate climate change.

398 citations


Journal ArticleDOI
TL;DR: Natural gas (NG) is a naturally gaseous hydrocarbon mixture that is formed under the earth's surface and is considered to be the cleanest fossil fuel and is a safe source of energy when transported, stored and used as mentioned in this paper.

382 citations


Journal ArticleDOI
06 Oct 2016-Nature
TL;DR: The largest isotopic methane source signature database so far, including fossil fuel, microbial and biomass-burning methane emission sources, finds that total fossil fuel methane emissions are not increasing over time, but are 60 to 110 per cent greater than current estimates owing to large revisions in isotope source signatures.
Abstract: Revisions in isotopic source signatures reveal that global total fossil fuel methane emissions from industry plus natural geological seepage are much larger than thought. Stefan Schwietzke et al. re-evaluate the global methane budget and the contribution of the fossil fuel industry to methane emissions on the basis of long-term global methane and methane carbon isotope records. They find that total fossil fuel methane emissions (fossil fuel industry plus natural geological methane seepage) are not increasing over time, but are 60–110 per cent greater than was previously thought. They also conclude that methane emissions from natural gas, oil and coal production and their usage are 20–60 per cent greater than inventories and that methane emissions from natural gas as a fraction of production have declined from about 8 per cent to 2 per cent over the past three decades. Methane has the second-largest global radiative forcing impact of anthropogenic greenhouse gases after carbon dioxide, but our understanding of the global atmospheric methane budget is incomplete. The global fossil fuel industry (production and usage of natural gas, oil and coal) is thought to contribute 15 to 22 per cent of methane emissions1,2,3,4,5,6,7,8,9,10 to the total atmospheric methane budget11. However, questions remain regarding methane emission trends as a result of fossil fuel industrial activity and the contribution to total methane emissions of sources from the fossil fuel industry and from natural geological seepage12,13, which are often co-located. Here we re-evaluate the global methane budget and the contribution of the fossil fuel industry to methane emissions based on long-term global methane and methane carbon isotope records. We compile the largest isotopic methane source signature database so far, including fossil fuel, microbial and biomass-burning methane emission sources. We find that total fossil fuel methane emissions (fossil fuel industry plus natural geological seepage) are not increasing over time, but are 60 to 110 per cent greater than current estimates1,2,3,4,5,6,7,8,9,10 owing to large revisions in isotope source signatures. We show that this is consistent with the observed global latitudinal methane gradient. After accounting for natural geological methane seepage12,13, we find that methane emissions from natural gas, oil and coal production and their usage are 20 to 60 per cent greater than inventories1,2. Our findings imply a greater potential for the fossil fuel industry to mitigate anthropogenic climate forcing, but we also find that methane emissions from natural gas as a fraction of production have declined from approximately 8 per cent to approximately 2 per cent over the past three decades.

374 citations


Journal ArticleDOI
TL;DR: In this article, a synthesis of the greenhouse gas methane from lakes and ponds is presented in the boreal region and northwards of the United States, where almost half of these waters are located.
Abstract: Lakes and ponds represent one of the largest natural sources of the greenhouse gas methane. By surface area, almost half of these waters are located in the boreal region and northwards. A synthesis ...

359 citations


Journal ArticleDOI
TL;DR: In this article, a review paper on strategies to reduce the carbonaceous deactivation of catalysts for improved DRM efficiency by appropriate catalyst development, operating conditions, and flow reactor designs is presented.
Abstract: Catalytic reforming of methane (CH4) with carbon dioxide (CO2), known as dry reforming of methane (DRM), produces synthesis gas, which is a mixture of hydrogen (H2) and carbon monoxide (CO). CH4 + CO2 → 2CO + 2H2, ΔH° = 247.3 kJ mol−1, ΔG = 61 770–67.32T. The DRM process has gained much attention recently as it reduces greenhouse gases (GHG), CO2 and CH4, in the atmosphere. In addition to reducing GHG, the DRM process produces valuable chemicals (CO + H2), provides a good approach to utilizing biogas and natural gas with a significant amount of CO2, has good capability as a chemical energy transmission system as compared to steam reforming, and finally yields the desired unity H2/CO ratio for Fischer–Tropsch synthesis. The bimetallic Ni-based catalysts supported on Al2O3/TiO2 and promoted with Ce/ZrO2 show remarkable performances in the DRM process. But, carbonaceous deactivation of the catalysts is the major problem faced during this process. Numerous studies have been cited on various aspects of DRM, and some papers are also devoted to reviewing carbonaceous deposition problems and their remedies. However, some lacunae exist, which are highlighted in the present review paper on strategies to reduce the carbonaceous deactivation of catalysts for improved DRM efficiency by appropriate catalyst development, operating conditions, and flow reactor designs. The disposal of spent catalysts falls under the category of hazardous industrial materials and is also required to comply with stringent environmental regulations. Therefore, regeneration and reclamation techniques for spent catalysts have also been discussed.

Journal ArticleDOI
TL;DR: In this article, the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483-498 K).
Abstract: The direct catalytic conversion of methane to liquid oxygenated compounds, such as methanol or dimethyl ether, at low temperature using molecular oxygen is a grand challenge in C–H activation that has never been met with synthetic, heterogeneous catalysts. We report the first demonstration of direct, catalytic oxidation of methane into methanol with molecular oxygen over copper-exchanged zeolites at low reaction temperatures (483–498 K). Reaction kinetics studies show sustained catalytic activity and high selectivity for a variety of commercially available zeolite topologies under mild conditions (e.g., 483 K and atmospheric pressure). Transient and steady state measurements with isotopically labeled molecules confirm catalytic turnover. The catalytic rates and apparent activation energies are affected by the zeolite topology, with caged-based zeolites (e.g., Cu-SSZ-13) showing the highest rates. Although the reaction rates are low, the discovery of catalytic sites in copper-exchanged zeolites will accele...

Journal ArticleDOI
28 Oct 2016-Science
TL;DR: A “super-dry” CH4 reforming reaction for enhanced CO production from CH4 and CO2 was developed, which resulted in higher CO production as compared with that of conventional dry reforming, by avoiding back reactions with water.
Abstract: Efficient CO2 transformation from a waste product to a carbon source for chemicals and fuels will require reaction conditions that effect its reduction. We developed a “super-dry” CH4 reforming reaction for enhanced CO production from CH4 and CO2. We used Ni/MgAl2O4 as a CH4-reforming catalyst, Fe2O3/MgAl2O4 as a solid oxygen carrier, and CaO/Al2O3 as a CO2 sorbent. The isothermal coupling of these three different processes resulted in higher CO production as compared with that of conventional dry reforming, by avoiding back reactions with water. The reduction of iron oxide was intensified through CH4 conversion to syngas over Ni and CO2 extraction and storage as CaCO3. CO2 is then used for iron reoxidation and CO production, exploiting equilibrium shifts effected with inert gas sweeping (Le Chatelier’s principle). Super-dry reforming uses up to three CO2 molecules per CH4 and offers a high CO space-time yield of 7.5 millimole CO per second per kilogram of iron at 1023 kelvin.

Journal ArticleDOI
05 Aug 2016-Science
TL;DR: Electrochemical integration of an electrochemical BaZrO3-based membrane exhibiting both proton and oxide ion conductivity into an MDA reactor gives rise to high aromatic yields and improved catalyst stability, and it is demonstrated that the electrochemical co-ionic membrane reactor enables high carbon efficiencies that improve the technoeconomic process viability.
Abstract: Nonoxidative methane dehydroaromatization (MDA: 6CH4 ↔ C6H6 + 9H2) using shape-selective Mo/zeolite catalysts is a key technology for exploitation of stranded natural gas reserves by direct conversion into transportable liquids. However, this reaction faces two major issues: The one-pass conversion is limited by thermodynamics, and the catalyst deactivates quickly through kinetically favored formation of coke. We show that integration of an electrochemical BaZrO3-based membrane exhibiting both proton and oxide ion conductivity into an MDA reactor gives rise to high aromatic yields and improved catalyst stability. These effects originate from the simultaneous extraction of hydrogen and distributed injection of oxide ions along the reactor length. Further, we demonstrate that the electrochemical co-ionic membrane reactor enables high carbon efficiencies (up to 80%) that improve the technoeconomic process viability.

Journal ArticleDOI
TL;DR: The isotopic evidence presented in this article suggests that the methane rise was dominated by significant increases in biogenic methane emissions, particularly in the tropics, for example, from expansion of tropical wetlands in years with strongly positive rainfall anomalies or emissions from increased agricultural sources such as ruminants and rice paddies.
Abstract: From 2007 to 2013, the globally averaged mole fraction of methane in the atmosphere increased by 5.7 ± 1.2 ppb yr−1. Simultaneously, δ13CCH4 (a measure of the 13C/12C isotope ratio in methane) has shifted to significantly more negative values since 2007. Growth was extreme in 2014, at 12.5 ± 0.4 ppb, with a further shift to more negative values being observed at most latitudes. The isotopic evidence presented here suggests that the methane rise was dominated by significant increases in biogenic methane emissions, particularly in the tropics, for example, from expansion of tropical wetlands in years with strongly positive rainfall anomalies or emissions from increased agricultural sources such as ruminants and rice paddies. Changes in the removal rate of methane by the OH radical have not been seen in other tracers of atmospheric chemistry and do not appear to explain short-term variations in methane. Fossil fuel emissions may also have grown, but the sustained shift to more 13C-depleted values and its significant interannual variability, and the tropical and Southern Hemisphere loci of post-2007 growth, both indicate that fossil fuel emissions have not been the dominant factor driving the increase. A major cause of increased tropical wetland and tropical agricultural methane emissions, the likely major contributors to growth, may be their responses to meteorological change.

Journal ArticleDOI
TL;DR: It is shown that when the particle size of zinc oxide is reduced down to the nanoscale, it exhibits high activity for methane oxidation under simulated sunlight illumination, and nano silver decoration further enhances the photo-activity via the surface plasmon resonance.
Abstract: The search for active catalysts that efficiently oxidize methane under ambient conditions remains a challenging task for both C1 utilization and atmospheric cleansing. Here, we show that when the particle size of zinc oxide is reduced down to the nanoscale, it exhibits high activity for methane oxidation under simulated sunlight illumination, and nano silver decoration further enhances the photo-activity via the surface plasmon resonance. The high quantum yield of 8% at wavelengths <400 nm and over 0.1% at wavelengths ∼470 nm achieved on the silver decorated zinc oxide nanostructures shows great promise for atmospheric methane oxidation. Moreover, the nano-particulate composites can efficiently photo-oxidize other small molecular hydrocarbons such as ethane, propane and ethylene, and in particular, can dehydrogenize methane to generate ethane, ethylene and so on. On the basis of the experimental results, a two-step photocatalytic reaction process is suggested to account for the methane photo-oxidation.

Journal ArticleDOI
TL;DR: The recent rapid rise in global methane concentrations is predominantly biogenic-most likely from agriculture-with smaller contributions from fossil fuel use and possibly wetlands as discussed by the authors, but the reasons for this renewed growth are still unclear, primarily because of uncertainties in the global methane budget.
Abstract: Unlike CO2, atmospheric methane concentrations are rising faster than at any time in the past two decades and, since 2014, are now approaching the most greenhouse-gas-intensive scenarios. The reasons for this renewed growth are still unclear, primarily because of uncertainties in the global methane budget. New analysis suggests that the recent rapid rise in global methane concentrations is predominantly biogenic-most likely from agriculture-with smaller contributions from fossil fuel use and possibly wetlands. Additional attention is urgently needed to quantify and reduce methane emissions. Methane mitigation offers rapid climate benefits and economic, health and agricultural co-benefits that are highly complementary to CO2 mitigation.

Journal ArticleDOI
TL;DR: A comprehensive review of the state of the art in the field of solid oxide fuel cells (SOFCs) can be found in this article, where the authors present an in-depth review with emphasis on electronic structure, charge transport and catalysis.

Journal ArticleDOI
TL;DR: In this article, the state-of-the-art in catalytic processes to convert methane (a major component of natural gas) to more valuable hydrocarbons as fuels or chemicals is reviewed.

Journal ArticleDOI
TL;DR: In this article, a unified model is established to describe gas-water-clay interactions, in which, gas-solid Langmuir equation and gas-liquid Gibbs equation are integrated by water coverage coefficient, and a mathematical model is presented to quantify thickness of water films by considering surface force interactions between liquid film and clay.

Journal ArticleDOI
TL;DR: Experiments of ambient pressure XPS indicate that methane dissociates on Ni/CeO2 at temperatures as low as 300 K, generating CHx and COx species on the surface of the catalyst.
Abstract: Ni-CeO2 is a highly efficient, stable and non-expensive catalyst for methane dry reforming at relative low temperatures (700 K). The active phase of the catalyst consists of small nanoparticles of nickel dispersed on partially reduced ceria. Experiments of ambient pressure XPS indicate that methane dissociates on Ni/CeO2 at temperatures as low as 300 K, generating CHx and COx species on the surface of the catalyst. Strong metal-support interactions activate Ni for the dissociation of methane. The results of density-functional calculations show a drop in the effective barrier for methane activation from 0.9 eV on Ni(111) to only 0.15 eV on Ni/CeO2-x (111). At 700 K, under methane dry reforming conditions, no signals for adsorbed CHx or C species are detected in the C 1s XPS region. The reforming of methane proceeds in a clean and efficient way.

Journal ArticleDOI
TL;DR: In this article, the tetrahydrofuran (THF) was used as a thermodynamic and kinetic promoter for methane hydrate formation in an unstirred tank reactor configuration.

Journal ArticleDOI
TL;DR: The scope of MOF materials with ultrahigh working capacity to include linkers having the common acrylate connectivity is expanded, and MOF-905 is among the best performing methane storage materials with a volumetric working capacity rivaling that of HKUST-1.
Abstract: High methane storage capacity in porous materials is important for the design and manufacture of vehicles powered by natural gas. Here, we report the synthesis, crystal structures and methane adsorption properties of five new zinc metal–organic frameworks (MOFs), MOF-905, MOF-905-Me2, MOF-905-Naph, MOF-905-NO2, and MOF-950. All these MOFs consist of the Zn4O(−CO2)6 secondary building units (SBUs) and benzene-1,3,5-tri-β-acrylate, BTAC. The permanent porosity of all five materials was confirmed, and their methane adsorption measured up to 80 bar to reveal that MOF-905 is among the best performing methane storage materials with a volumetric working capacity (desorption at 5 bar) of 203 cm3 cm–3 at 80 bar and 298 K, a value rivaling that of HKUST-1 (200 cm3 cm–3), the benchmark compound for methane storage in MOFs. This study expands the scope of MOF materials with ultrahigh working capacity to include linkers having the common acrylate connectivity.

Journal ArticleDOI
TL;DR: Effect of biochar addition on hydrogen and methane production in two-phase anaerobic digestion of aqueous carbohydrates was studied using bench-scale bioreactors andBiochar addition enhanced VFA generation during hydrogen production and VFA degradation in methane production.

Journal ArticleDOI
TL;DR: In this paper, the authors review the value of current, future, and proposed satellite observations to better quantify and understand methane emissions through inverse analyses, from the global scale down to the scale of point sources and in combination with suborbital (surface and aircraft) data.
Abstract: . Methane is a greenhouse gas emitted by a range of natural and anthropogenic sources. Atmospheric methane has been measured continuously from space since 2003, and new instruments are planned for launch in the near future that will greatly expand the capabilities of space-based observations. We review the value of current, future, and proposed satellite observations to better quantify and understand methane emissions through inverse analyses, from the global scale down to the scale of point sources and in combination with suborbital (surface and aircraft) data. Current global observations from Greenhouse Gases Observing Satellite (GOSAT) are of high quality but have sparse spatial coverage. They can quantify methane emissions on a regional scale (100–1000 km) through multiyear averaging. The Tropospheric Monitoring Instrument (TROPOMI), to be launched in 2017, is expected to quantify daily emissions on the regional scale and will also effectively detect large point sources. A different observing strategy by GHGSat (launched in June 2016) is to target limited viewing domains with very fine pixel resolution in order to detect a wide range of methane point sources. Geostationary observation of methane, still in the proposal stage, will have the unique capability of mapping source regions with high resolution, detecting transient "super-emitter" point sources and resolving diurnal variation of emissions from sources such as wetlands and manure. Exploiting these rapidly expanding satellite measurement capabilities to quantify methane emissions requires a parallel effort to construct high-quality spatially and sectorally resolved emission inventories. Partnership between top-down inverse analyses of atmospheric data and bottom-up construction of emission inventories is crucial to better understanding methane emission processes and subsequently informing climate policy.

Journal ArticleDOI
TL;DR: This paper used nuclear magnetic resonance spectroscopy to show that polysaccharide esters of three phosphonic acids are important constituents of dissolved organic matter in seawater from the North Pacific.
Abstract: A lot of methane is emitted from oxygenated seawater, where its production should be inhibited. Seawater incubations and organic matter characterizations reveal that bacteria aerobically produce methane from phosphonates in organic matter. Biogenic methane is widely thought to be a product of archaeal methanogenesis, an anaerobic process that is inhibited or outcompeted by the presence of oxygen and sulfate1,2,3. Yet a large fraction of marine methane delivered to the atmosphere is produced in high-sulfate, fully oxygenated surface waters that have methane concentrations above atmospheric equilibrium values, an unexplained phenomenon referred to as the marine methane paradox4,5. Here we use nuclear magnetic resonance spectroscopy to show that polysaccharide esters of three phosphonic acids are important constituents of dissolved organic matter in seawater from the North Pacific. In seawater and pure culture incubations, bacterial degradation of these dissolved organic matter phosphonates in the presence of oxygen releases methane, ethylene and propylene gas. Moreover, we found that in mutants of a methane-producing marine bacterium, Pseudomonas stutzeri, disrupted in the C–P lyase phosphonate degradation pathway, methanogenesis was also disabled, indicating that the C–P lyase pathway can catalyse methane production from marine dissolved organic matter. Finally, the carbon stable isotope ratio of methane emitted during our incubations agrees well with anomalous isotopic characteristics of seawater methane. We estimate that daily cycling of only about 0.25% of the organic matter phosphonate inventory would support the entire atmospheric methane flux at our study site. We conclude that aerobic bacterial degradation of phosphonate esters in dissolved organic matter may explain the marine methane paradox.

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TL;DR: In this article, the catalytic properties of Fe 2 O 3 to metallic Fe, followed by carburization of the metallic species, were investigated in the absence of an added oxidant.

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TL;DR: In this paper, a series of methane adsorption isotherms were measured at 35.4°C, 50.6°C and 65.4°C at pressures up to 15.74%.

Journal ArticleDOI
18 Mar 2016-Science
TL;DR: Analysis of methane and ethane data from dozens of plume transects, collected during 13 research-aircraft flights between 7 November 2015 and 13 February 2016, shows atmospheric leak rates of up to 60 metric tons of methaneand ethane per hour.
Abstract: Single-point failures of natural gas infrastructure can hamper methane emission control strategies designed to mitigate climate change. The 23 October 2015 blowout of a well connected to the Aliso Canyon underground storage facility in California resulted in a massive release of natural gas. Analysis of methane and ethane data from dozens of plume transects, collected during 13 research-aircraft flights between 7 November 2015 and 13 February 2016, shows atmospheric leak rates of up to 60 metric tons of methane and 4.5 metric tons of ethane per hour. At its peak, this blowout effectively doubled the methane emission rate of the entire Los Angeles basin and, in total, released 97,100 metric tons of methane to the atmosphere.

Journal ArticleDOI
TL;DR: In-situ synchrotron X-ray computed microtomography with sub-micrometer voxel size was used to study the decomposition of gas hydrates in a sedimentary matrix.
Abstract: In-situ synchrotron X-ray computed microtomography with sub-micrometer voxel size was used to study the decomposition of gas hydrates in a sedimentary matrix. Xenon-hydrate was used instead of methane hydrate to enhance the absorption contrast. The microstructural features of the decomposition process were elucidated indicating that the decomposition starts at the hydrate-gas interface; it does not proceed at the contacts with quartz grains. Melt water accumulates at retreating hydrate surface. The decomposition is not homogeneous and the decomposition rates depend on the distance of the hydrate surface to the gas phase indicating a diffusion-limitation of the gas transport through the water phase. Gas is found to be metastably enriched in the water phase with a concentration decreasing away from the hydrate-water interface. The initial decomposition process facilitates redistribution of fluid phases in the pore space and local re-formation of gas hydrates. The observations allow also rationalizing earlier conjectures from experiments with low spatial resolutions and suggest that the hydrate-sediment assemblies remain intact until the hydrate spacers between sediment grains finally collapse; possible effects on mechanical stability and permeability are discussed. The resulting time resolved characteristics of gas hydrate decomposition and the influence of melt water on the reaction rate are of importance for a suggested gas recovery from marine sediments by depressurization. This article is protected by copyright. All rights reserved.