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Methane
Kinds of Methane Terms modified by Methane Selected AbstractsNative wildlife on rangelands to minimize methane and produce lower-emission meat: kangaroos versus livestockCONSERVATION LETTERS, Issue 3 2008George R. Wilson Abstract Ruminant livestock produce the greenhouse gas methane and so contribute to global warming and biodiversity reduction. Methane from the foregut of cattle and sheep constitutes 11% of Australia's total greenhouse gas emissions (GHG). Kangaroos, on the other hand, are nonruminant forestomach fermenters that produce negligible amounts of methane. We quantified the GHG savings Australia could make if livestock were reduced on the rangelands where kangaroo harvesting occurs and kangaroo numbers increased to 175 million to produce same amount of meat. Removing 7 million cattle and 36 million sheep by 2020 would lower Australia's GHG emissions by 16 megatonnes, or 3% of Australia's annual emissions. However, the change will require large cultural and social adjustments and reinvestment. Trials are underway based on international experiences of managing free-ranging species. They are enabling collaboration between farmers, and if they also show benefits to sustainability, rural productivity, and conservation of biodiversity, they could be expanded to incorporate change on the scale of this article. Farmers have few options to reduce the contribution that livestock make to GHG production. Using kangaroos to produce low-emission meat is an option for the Australian rangelands which would avoid permit fees under Australia's Emissions Trading Scheme, and could even have global application. [source] Detecting active methanogenic populations on rice roots using stable isotope probingENVIRONMENTAL MICROBIOLOGY, Issue 3 2005Yahai Lu Summary Methane is formed on rice roots mainly by CO2 reduction. The present study aimed to identify the active methanogenic populations responsible for this process. Soil-free rice roots were incubated anaerobically under an atmosphere of H2/13CO2 or N2/13CO2 with phosphate or carbonate (marble) as buffer medium. Nucleic acids were extracted and fractionated by caesium trifluoroacetate equilibrium density gradient centrifugation after 16-day incubation. Community analyses were performed for gradient fractions using terminal restriction fragment polymorphism analysis (T-RFLP) and sequencing of the 16S rRNA genes. In addition, rRNA was extracted and analysed at different time points to trace the community change during the 16-day incubation. The Methanosarcinaceae and the yet-uncultured archaeal lineage Rice Cluster-I (RC-I) were predominant in the root incubations when carbonate buffer and N2 headspace were used. The analysis of [13C]DNA showed that the relative 16S rRNA gene abundance of RC-I increased whereas that of the Methanosarcinaceae decreased with increasing DNA buoyant density, indicating that members of RC-I were more active than the Methanosarcinaceae. However, an unexpected finding was that RC-I was suppressed in the presence of high H2 concentrations (80%, v/v), which during the early incubation period caused a lower CH4 production compared with that with N2 in the headspace. Eventually, however, CH4 production increased, probably because of the activity of Methanosarcinaceae, which became prevalent. Phosphate buffer appeared to inhibit the activity of the Methanosarcinaceae, resulting in lower CH4 production as compared with carbonate buffer. Under these conditions, Methanobacteriaceae were the prevalent methanogens. Our study suggests that the active methanogenic populations on rice roots change in correspondence to the presence of H2 (80%, v/v) and the type of buffer used in the system. [source] The Reductive Elimination of Methane from ansa -Hydrido(methyl)metallocenes of Molybdenum and Tungsten: Application of Hammond's Postulate to Two-State ReactionsEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 15 2005José-Luis Carreón-Macedo Abstract The energetic profile of the methane reductive elimination from a selected number of hydrido(methyl)molybdenocene and -tungstenocene derivatives has been calculated by DFT methods. The calculations were carried out for the CH2(C5H4)2M (a -M), SiH2(C5H4)2M (a -H2Si,M), and SiMe2(C5Me4)2M (a -Me2Si,M*) ansa -metallocene systems for M = Mo, W. They include the full optimization of minima [the hydrido(methyl) starting complexes, M(H)(CH3), the intermediate methane complexes, M(CH4), and the metallocene products in the singlet and triplet configurations, (3M and 1M)], transition states (for the methyl hydride reductive elimination, M,TSins, and for the hydrogen exchange, M,TSexch), and the minimum energy crossing point (M,MECP) leading from the singlet methane complexes to the corresponding triplet metallocenes. The results are compared with those previously obtained for the simpler (C5H5)2M (Cp2M) systems (J. C. Green, J. N. Harvey, and R. Poli, J. Chem. Soc., Dalton Trans.2002, 1861). The calculated energy profiles, notably the relative energies of M,TSins and M,MECP, are in agreement with available experimental observations for the a -Me2Si,M* systems. The comparison of the energies and geometries of the rate-determining M,TSins and M,MECP structures with those of the thermodynamically relevant minima for the various systems show the applicability of Hammond's postulate to two-state reactions. However, one notable exception serves to show that the principle is only quantitatively reliable when all the potential energy surfaces for the set of analogous reactions have similar shapes. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Methane and nitrous oxide fluxes from a farmed Swedish HistosolEUROPEAN JOURNAL OF SOIL SCIENCE, Issue 3 2009Å. Kasimir Klemedtsson Summary Fluxes of the greenhouse gases methane (CH4) and nitrous oxide (N2O) from histosolic soils (which account for approximately 10% of Swedish agricultural soils) supporting grassley and barley production in Sweden were measured over 3 years using static chambers. Emissions varied both over area and time. Methane was both produced and oxidized in the soil: fluxes were small, with an average emission of 0.12 g CH4 m,2 year,1 at the grassley site and net uptake of ,0.01 g CH4 m,2 year,1 at the barley field. Methane emission was related to soil water, with more emission when wet. Nitrous oxide emissions varied, with peaks of emission after soil cultivation, ploughing and harrowing. On average, the grassley and barley field had emissions of 0.20 and 1.51 g N2O m,2 year,1, respectively. We found no correlation between N2O and soil factors, but the greatest N2O emission was associated with the driest areas, with < 60% average water-filled pore space. We suggest that the best management option to mitigate emissions is to keep the soil moderately wet with permanent grass production, which restricts N2O emissions whilst minimizing those of CH4. [source] Methane and nitrous oxide fluxes of soils in pure and mixed stands of European beech and Norway spruceEUROPEAN JOURNAL OF SOIL SCIENCE, Issue 5 2006W. Borken Summary Tree species can affect the sink and source strength of soils for atmospheric methane and nitrous oxide. Here we report soil methane (CH4) and nitrous oxide (N2O) fluxes of adjacent pure and mixed stands of beech and spruce at Solling, Germany. Mean CH4 uptake rates ranged between 18 and 48 ,g C m,2 hour,1 during 2.5 years and were about twice as great in both mixed and the pure beech stand as in the pure spruce stand. CH4 uptake was negatively correlated with the dry mass of the O horizon, suggesting that this diminishes the transport of atmospheric CH4 into the mineral soil. Mean N2O emission was rather small, ranging between 6 and 16 ,g N m,2 hour,1 in all stands. Forest type had a significant effect on N2O emission only in one mixed stand during the growing season. We removed the O horizon in additional plots to study its effect on gas fluxes over 1.5 years, but N2O emissions were not altered by this treatment. Surprisingly, CH4 uptake decreased in both mixed and the pure beech stands following the removal of the O horizon. The decrease in CH4 uptake coincided with an increase in the soil moisture content of the mineral soil. Hence, O horizons may maintain the gas diffusivity within the mineral soil by storing water which cannot penetrate into the mineral soil after rainfall. Our results indicate that conversion of beech forests to beech,spruce and pure spruce forests could decrease soil CH4 uptake, while the long-term effect on N2O emissions is expected to be rather small. [source] Niches of the pre-photosynthetic biosphere and geologic preservation of Earth's earliest ecologyGEOBIOLOGY, Issue 2 2007NORMAN H. SLEEP ABSTRACT The tree of terrestrial life probably roots in non-photosynthetic microbes. Chemoautotrophs were the first primary producers, and the globally dominant niches in terms of primary productivity were determined by availability of carbon dioxide and hydrogen for methanogenesis and sulfite reduction. Methanogen niches were most abundant where CO2 -rich ocean water flowed through serpentinite. Black smoker vents from basalt supplied comparable amount of H2. Hydrogen from arc volcanoes supported a significant methanogenic niche at the Earth's surface. SO2 from arc volcanoes reacted with organic matter and hydrogen, providing a significant surface niche. Methane ascended to the upper atmosphere where photolysis produced C-rich haze and CO, and H escaped into space. The CO and C-rich haze supported secondary surface niches. None of these ecologies were bountiful; less than 1% of the CO2 vented by ridge axes, arcs, and metamorphism became organic matter before it was buried in carbonate. In contrast, a photosynthetic biosphere leaves copious amounts of organic carbon, locally concentrated in sediments. Black shales are a classic geologic biosignature for photosynthesis that can survive subduction and high-grade metamorphism. [source] Biogenic gas production from major Amazon reservoirs, BrazilHYDROLOGICAL PROCESSES, Issue 7 2003Luiz Pinguelli Rosa Abstract Methane (CH4) and carbon dioxide (CO2) emissions from Brazilian reservoirs were assessed. Point measurements were made during 1998 and 1999 (using inverted funnels for bubbles and air and water concentration gradients for diffusion) in the 559 km2 Samuel reservoir, which was initially flooded in 1988, and the 2430 km2 Tucuruí reservoir, which was flooded in 1984, and the data were evaluated with respect to historical measurements in other Brazilian reservoirs. Bubble emissions of CH4 were higher in Samuel (ranging from 2 to 70 mgCH4 m,2 day,1) than in Tucuruí (ranging from 0·5 to 30 mgCH4 m,2 day,1), with the highest values occurring the shallowest regions in each reservoir. CH4 from diffusion for the Tucuruí reservoir ranged from 5 to 30 mgCH4 m,2 day,1, which is lower than that for the Samuel reservoir, which ranged from 10 to 80 mgCH4 m,2 day,1. The smaller emissions in Tucuruí compared with Samuel are attributed to a larger depletion in the source organic material that was present when the reservoir was filled. The CO2 concentration was similar for each reservoir, and ranged from 1000 to 10 000 mgCO2 m,2 day,1. Copyright © 2003 John Wiley & Sons, Ltd. [source] A High-Yield, Liquid-Phase Approach for the Partial Oxidation of Methane to Methanol using SO3 as the OxidantADVANCED SYNTHESIS & CATALYSIS (PREVIOUSLY: JOURNAL FUER PRAKTISCHE CHEMIE), Issue 9 2005Sudip Mukhopadhyay Abstract A direct approach for producing methanol from methane in a three-step, liquid phase process is reported. In the first step, methane is reacted with SO3 to form methanesulfonic acid (MSA) at 75,°C using a free-radical initiator and MSA as the solvent. Urea-H2O2 in combination with RhCl3 is found to be the most effective initiator (57% conversion of SO3; 7.2% conversion of CH4). MSA is then oxidized by SO3 at 160,°C in a second step to produce a mixture containing methyl bisulfate and some methyl methanesulfonate (87% conversion of MSA). In the third step, the mixture of methyl bisulfate and methyl methanesulfonate is hydrolyzed in the presence of an organic solvent, to produce an organic phase containing methanol and an aqueous phase containing sulfuric acid and some MSA (63% conversion of methyl bisulfate; 72% conversion of methyl methanesulfonate). Overall, 58% of the MSA (of which 23% is derived from methane) is converted to methanol. [source] Steady-state multiplicity, flashback, and control issues in CH4 radiant burnersAICHE JOURNAL, Issue 9 2004M. Bizzi Abstract Methane is widely employed as a source of energy in combustion systems. Among the currently available technologies, radiant heaters offer high thermal efficiency and low environmental impact in comparison with atmospheric burners. The present work deals with the modeling of methane combustion in a noncatalytic metal fiber burner, represented by means of one-dimensional transient equations. The model accounts for a detailed reaction mechanism, radiation within the porous medium, longitudinal heat and mass transfer. After its validation, the model was employed to analyze a typical stability problem that affects these systems: under given operating conditions (low specific power inputs and excess of air) the occurrence of flashback may in fact preclude the safe operation of the system. As a consequence of energy radiation in the upstream direction, the burner upstream surface and the plenum chamber might become hot enough to heat in turn the gas feedstock, thus eventually determining flashback. In this paper, the mechanism of flashback is numerically investigated as a function of the burner structure and operating conditions by means of a model analysis so as to single out regions of flashback occurrence and a criterion for safe operation. Finally, some guidelines are outlined for a cheap and effective control of the system, paving the way for possible improvement of currently adopted control systems. © 2004 American Institute of Chemical Engineers AIChE J, 50: 2276,2286, 2004 [source] Catalytic Effects of Metals on the Conversion of Methane in Gliding DischargesPLASMA PROCESSES AND POLYMERS, Issue 7-8 2007Krzysztof Schmidt-Sza, owski Abstract Plasma-catalytic methane conversion was studied under gliding-discharge conditions using a mobile (spouted) catalytic bed of fine particles. A new model of the GD reactor was tested for the non-oxidative methane coupling using alumina-supported catalysts containing Cu, Ni, Ag or Pt resistant against the plasma action. C2 hydrocarbons, besides hydrogen, were the main products, with some amounts of non-volatile substances (mainly soot). With Cu/Al2O3, Ni/Al2O3, Ag/Al2O3, and alumina beds, acetylene was mainly produced from the CH4,+,H2 mixture with none or a minor share of other C2 hydrocarbons. Using Pt/Al2O3, an increased ethylene and ethane content was found with lower acetylene content. [source] Isotope applications in environmental investigations part II: Groundwater age dating and recharge processes, and provenance of sulfur and methaneREMEDIATION, Issue 2 2003Julie K. Sueker Measurement of the isotopic composition of solids, solutes, gases, and water complement standard hydrogeological investigation techniques by providing information that may not otherwise be obtainable. Groundwater age estimates determined from the decay of radio-isotopes or from groundwater concentrations of anthropogenic gases such as chlorofluorocarbons (CFCs) and sulfur hexafluoride (SF6) are used to verify flow regimes and constrain or calibrate hydrologic flow models. Groundwater recharge rates are estimated by measuring the concentrations or activities of a variety of isotopes including 2H, 3H, 18O, and 36Cl. Excess sulfur causes salinization of water supplies and acidification of precipitation, surface water, and groundwater. The wide range of sulfur isotopic compositions exhibited by different sulfur species and sources allows the application of sulfur isotopes to trace sources and fate of sulfur in the environment. Methane is a ubiquitous gas that has economic value when located in extractable reservoirs. Methane is also a greenhouse gas and is a potential explosion and health hazard when it accumulates in buildings and water distribution systems. The carbon and hydrogen isotopic composition of methane can be used to determine the provenance of methane, distinguishing between thermogenic and biogenic sources. The addition of isotopic analyses to environmental investigations can be a cost-effective means of resolving intractable issues. © 2003 Wiley Periodicals, Inc. [source] Oxidative Coupling of Methane in a Negative DC Corona Reactor at Low TemperatureTHE CANADIAN JOURNAL OF CHEMICAL ENGINEERING, Issue 1 2003Faezeh Bagheri-Tar Abstract Oxidative coupling of methane (OCM) in the presence of DC corona is reported in a narrow glass tube reactor at atmospheric pressure and at temperatures below 200°C. The corona is created by applying 2200V between a tip and a plate electrode 1.5 mm apart. The C2 selectivity as well as the methane conversion are functions of methane-to-oxygen ratio, gas residence time, and electric current. At CH4/O2 ratio of 5 and the residence time of about 30 ms, a C2 yield of 23.1% has been achieved. The main products of this process are ethane, ethylene, acetylene as well as CO and CO2 with CO/CO2 ratios as high as 25. It is proposed that methane is activated by electrophilic oxygen species to form methyl radicals and C2 products are produced by a consecutive mechanism, whereas COx is formed during parallel reactions. On décrit le couplage oxydant du méthane (OCM) en présence d'une couronne CC dans un réacteur tubulaire étroit en verre à la pression atmosphérique et à des températures en dessous de 200°C. La couronne est créée en appliquant 2200 V entre une pointe et une électrode plate distantes de 1,5 mm. La sélectivité du C2 ainsi que la conversion du méthane sont des fonctions du rapport méthane-oxygène, du temps de séjour du gaz et du courant électrique. À un rapport de CH4/O2 de 5 et un temps de séjour d'environ 30 ms, un rendement de C2 de 23,1 % est obtenu. Les principaux produits de ce procédé sont l'éthane, l'éthylène, l'acétylène, ainsi que le CO et le CO2 avec des rapports de CO/CO2 aussi élevés que 25. On propose l'idée que le méthane est activé par des espèces d'oxygène électrophiles pour former des radicaux de méthyle et que les produits du C2 sont produits par un mécanisme consécutif, tandis que les COx se forment lors de réactions parallèles. [source] Mechanistic Study of Partial Oxidation of Methane to Syngas Using In Situ Time-Resolved FTIR and Microprobe Raman SpectroscopiesTHE CHEMICAL RECORD, Issue 2 2002Mechanism of Methane Partial Oxidation Abstract In situ time-resolved Fourier transform infrared (FTIR) and microprobe Raman spectroscopies were used to characterize the reaction mechanisms of the partial oxidation of methane to syngas over SiO2 - and ,-Al2O3 -supported rhodium and ruthenium catalysts. The interaction of both pure methane and a methane/oxygen mixture at a stoichiometric feed ratio with an oxygen-rich catalyst surface led to the formation of CO2 and H2O as the primary products. For the H2 -pretreated samples, the reaction mechanisms with the catalysts differ. Only Rh/SiO2 is capable of catalyzing the direct oxidation of methane to syngas, while syngas formation over Rh/g-Al2O3, Ru/SiO2, and Ru/g-Al2O3 can be achieved mainly via a combustion-reforming scheme. The significant difference in the mechanisms for partial oxidation of methane to syngas over the catalysts can be correlated to the differences in the concentration of oxygen species (O2,) on the catalyst surface during the reaction, mainly due to the difference in the nature of the metals and supports. © 2002 The Japan Chemical Journal Forum and Wiley Periodicals, Inc. Chem Rec 2:102,112, 2002: Published online in Wiley InterScience (www.interscience.wiley.com) DOI 10.1002/tcr.10016 [source] Factors affecting methane production and mitigation in ruminantsANIMAL SCIENCE JOURNAL, Issue 1 2010Masaki SHIBATA ABSTRACT Methane (CH4) is the second most important greenhouse gas (GHG) and that emitted from enteric fermentation in livestock is the single largest source of emissions in Japan. Many factors influence ruminant CH4 production, including level of intake, type and quality of feeds and environmental temperature. The objectives of this review are to identify the factors affecting CH4 production in ruminants, to examine technologies for the mitigation of CH4 emissions from ruminants, and to identify areas requiring further research. The following equation for CH4 prediction was formulated using only dry matter intake (DMI) and has been adopted in Japan to estimate emissions from ruminant livestock for the National GHG Inventory Report: Y = ,17.766 + 42.793X , 0.849X2, where Y is CH4 production (L/day) and X is DMI (kg/day). Technologies for the mitigation of CH4 emissions from ruminants include increasing productivity by improving nutritional management, the manipulation of ruminal fermentation by changing feed composition, the addition of CH4 inhibitors, and defaunation. Considering the importance of ruminant livestock, it is essential to establish economically feasible ways of reducing ruminant CH4 production while improving productivity; it is therefore critical to conduct a full system analysis to select the best combination of approaches or new technologies to be applied under long-term field conditions. [source] Effect of cyclodextrin diallyl maleate on methane production, ruminal fermentation and microbes in vitro and in vivoANIMAL SCIENCE JOURNAL, Issue 1 2004Zeenat Ara LILA ABSTRACT Effects of ,-cyclodextrin diallyl maleate (CD-M) on methane production, ruminal fermentation and digestibility were studied both in vitro and in vivo. In in vitro study, diluted ruminal fluid (30 mL) was incubated anaerobically at 38°C for 6 and 24 h with or without CD-M using hay plus concentrate (1.5:1) as a substrate. The CD-M was added at different concentrations (0, 1.25, 2.5, 5.0 and 7.5 g/L). The pH of the medium and numbers of protozoa were not affected by the addition of CD-M. Total volatile fatty acids were increased and ammonia-N was decreased, molar proportion of acetate was decreased and propionate was increased (P < 0.05) by CD-M. Methane was inhibited (P < 0.05) by 14,76%. The effect of CD-M on methane production and ruminal fermentation was further investigated in vivo using four Holstein steers in a cross-over design. The steers were fed Sudangrass hay and concentrate mixture (1.5:1) with or without CD-M (2% of feed dry matter) as a supplement. Ruminal proportion of acetate tended to decrease and that of propionate was increased (P < 0.05) 2 h after CD-M dosing. Total viable counts, cellulolytic, sulfate reducing, acetogenic bacteria and protozoa were unaffected while methanogenic bacteria were decreased (P < 0.05) by CD-M. The plasma concentration of glucose was increased, whereas that of urea-N was decreased (P < 0.05). Methane was inhibited (P < 0.05) from 36.4 to 30.1 L/kg dry matter intake by the addition of CD-M. Apparent digestibilities of dry matter and neutral detergent fiber were not affected while that of crude protein was increased (P < 0.05) in the medicated steers. These data suggested that dietary supplementation of CD-M decreased methane production and improved nutrient use. [source] A review of biogas purification processesBIOFUELS, BIOPRODUCTS AND BIOREFINING, Issue 1 2009Nicolas Abatzoglou Abstract Biogas is a valuable renewable energy carrier. It can be exploited directly as a fuel or as a raw material for the production of synthesis gas and/or hydrogen. Methane (CH4) and carbon dioxide (CO2) are the main constituents, but biogases also contain significant quantities of undesirable compounds (contaminants), such as hydrogen sulfide (H2S), ammonia (NH3) and siloxanes. The existence and quantities of these contaminants depend on the biogas source (i.e., landfills, anaerobic fermentation of manure). Their presence constitutes a major problem because (i) they can be detrimental to any biogas thermal or thermocatalytic conversion device (e.g., corrosion, erosion, fouling); and (ii) they generate harmful environmental emissions. It is therefore important to include biogas purification steps upstream of its final use processes. This review is aimed at presenting the scientific and technical state-of-theart in biogas purification processes. Both mature, already-applied and promising, under-development technologies are reported and described here. © 2008 Society of Chemical Industry and John Wiley & Sons, Ltd [source] High-pressure systems for gas-phase free continuous incubation of enriched marine microbial communities performing anaerobic oxidation of methaneBIOTECHNOLOGY & BIOENGINEERING, Issue 3 2010Christian Deusner Abstract Novel high-pressure biotechnical systems that were developed and applied for the study of anaerobic oxidation of methane (AOM) are described. The systems, referred to as high-pressure continuous incubation system (HP-CI system) and high-pressure manifold-incubation system (HP-MI system), allow for batch, fed-batch, and continuous gas-phase free incubation at high concentrations of dissolved methane and were designed to meet specific demands for studying environmental regulation and kinetics as well as for enriching microbial biomass in long-term incubation. Anoxic medium is saturated with methane in the first technical stage, and the saturated medium is supplied for biomass incubation in the second stage. Methane can be provided in continuous operation up to 20,MPa and the incubation systems can be operated during constant supply of gas-enriched medium at a hydrostatic pressure up to 45,MPa. To validate the suitability of the high-pressure systems, we present data from continuous and fed-batch incubation of highly active samples prepared from microbial mats from the Black Sea collected at a water depth of 213,m. In continuous operation in the HP-CI system initial methane-dependent sulfide production was enhanced 10- to 15-fold after increasing the methane partial pressure from near ambient pressure of 0.2 to 10.0,MPa at a hydrostatic pressure of 16.0,MPa in the incubation stage. With a hydraulic retention time of 14,h a stable effluent sulfide concentration was reached within less than 3 days and a continuing increase of the volumetric AOM rate from 1.2 to 1.7,mmol,L,1,day,1 was observed over 14 days. In fed-batch incubation the AOM rate increased from 1.5 to 2.7 and 3.6,mmol,L,1,day,1 when the concentration of aqueous methane was stepwise increased from 5 to 15,mmol,L,1 and 45,mmol,L,1. A methane partial pressure of 6,MPa and a hydrostatic pressure of 12,MPa in manifold fed-batch incubation in the HP-MI system yielded a sixfold increase in the volumetric AOM rate. Over subsequent incubation periods AOM rates increased from 0.6 to 1.2,mmol,L,1,day,1 within 26 days of incubation. No inhibition of biomass activity was observed in all continuous and fed-batch incubation experiments. The organisms were able to tolerate high sulfide concentrations and extended starvation periods. Biotechnol. Bioeng. 2010; 105: 524,533. © 2009 Wiley Periodicals, Inc. [source] Kinetic Reaction Models for the Selective Reduction of NO by Methane over Multifunctional Zeolite-based Redox CatalystsCHEMICAL ENGINEERING & TECHNOLOGY (CET), Issue 12 2004T. Sowade Abstract Kinetic measurements of the selective catalytic reduction (SCR) of NO by methane were performed over CeO2/H-ZSM-5, In-ZSM-5, and CeO2/In-ZSM-5 catalysts. The parameter space covered NO, CH4, and O2 concentrations varying from 250 to 1000 ppm, from 500 to 2000 ppm, and from 0.5 to 10,vol.-%, respectively, space velocities between 5000 and 90000 h,1 and temperatures between 573 and 873 K depending on the catalyst activities. With CeO2/In-ZSM-5 an additional series of measurements was performed with moistened feed gas (0.5,10,vol.-% H2O). On the basis of a pseudo-homogeneous, one-dimensional fixed-bed reactor model, the data were fitted to a kinetic model that includes power rate laws for the reduction of NO and for the unselective total oxidation of methane. From analyses of isothermal data sets, almost all reaction orders were found to vary significantly with changing temperature, which indicates that the simple kinetic model cannot reflect the complex reaction mechanism correctly. Nevertheless, the data measured with In-ZSM-5 could be modeled with good accuracy over a wide range of reaction temperatures (150 K) while the accuracy was less satisfactory with the remaining data sets, in particular for data with the moist feed over CeO2/In-ZSM-5. With the latter catalyst it was not possible to represent the data measured in dry and in moist feed in a single model even upon confinement to fixed reaction temperatures. A comparison of the separate models established showed strong changes in the reaction orders in the presence of water, which occur apparently already at a very low water content (,,0.5,vol.-%). The kinetic parameters found are in agreement with earlier conclusions about the reaction mechanisms. With In-ZSM-5, both reaction orders and the activation energy show a rate-limiting influence of NO oxidation on the NO reduction path which is removed by the presence of the CeO2 promoter. A difference in the reaction mechanism over CeO2/In-ZSM-5 and CeO2/H-ZSM-5 is reflected in different kinetic parameters. The differences of the kinetic parameters between dry-feed and moist-feed models for CeO2/In-ZSM-5 reflect adsorption competition between the reactants and water. [source] ChemInform Abstract: Production of Hydrogen from Reactions of Methane with Boranes.CHEMINFORM, Issue 5 2010Saartje Swinnen Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Hydrogen-Atom Abstraction from Methane by Stoichiometric Vanadium,Silicon Heteronuclear Oxide Cluster CationsCHEMISTRY - A EUROPEAN JOURNAL, Issue 37 2010Dr. Xun-Lei Ding Abstract Vanadium,silicon heteronuclear oxide cluster cations were prepared by laser ablation of a V/Si mixed sample in an O2 background. Reactions of the heteronuclear oxide cations with methane in a fast-flow reactor were studied with a time-of-flight (TOF) mass spectrometer to detect the cluster distribution before and after the reactions. Hydrogen abstraction reactions were identified over stoichiometric cluster cations [(V2O5)n(SiO2)m]+ (n=1, m=1,4; n=2, m=1), and the estimated first-order rate constants for the reactions were close to that of the homonuclear oxide cluster V4O10+ with methane. Density functional calculations were performed to study the structural, bonding, electronic, and reactivity properties of these stoichiometric oxide clusters. Terminal-oxygen-centered radicals (Ot.) were found in all of the stable isomers. These Ot. radicals are active sites of the clusters in reaction with CH4. The Ot. radicals in [V2O5(SiO2)1,4]+ clusters are bonded with Si rather than V atoms. All the hydrogen abstraction reactions are favorable both thermodynamically and kinetically. This work reveals the unique properties of metal/nonmetal heteronuclear oxide clusters, and may provide new insights into CH4 activation on silica-supported vanadium oxide catalysts. [source] The Anomalous Deuterium Isotope Effect in the NMR Spectrum of Methane: An Analysis in Localized Molecular OrbitalsCHEMPHYSCHEM, Issue 9 2008Stephan P. A. Sauer Prof. Dr. Anomaly explained: The secondary isotope effect on the carbon,hydrogen indirect nuclear spin,spin coupling constant in methane, which is larger than the primary isotope effect, is explained in terms of contributions to the coupling constant from localized molecular orbitals. [source] Autothermal Reforming and Partial Oxidation of Methane in Fluidized Reactor over Highly Dispersed Ni Catalyst Prepared from Ni ComplexCHINESE JOURNAL OF CHEMISTRY, Issue 6 2006Jing Gao Abstract Highly dispersed Ni catalysts on spherical SiO2 were prepared by simple impregnation of Ni(acac)2, [Ni-(NH3)6,n(H2O)n]2+, [Ni(en)3]2+ and [Ni(EDTA)]2,. Pulse adsorption of H2 and TEM analysis results confirmed that Ni was dispersed very well on the surface of SiO2 even after calcination (4 h) and reduction (1 h) at high temperature of 800 °C. These highly dispersed and uniquely sized Ni crystallites were more stable and more reactive for both autothermal reforming and partial oxidation of methane in fluidized reactor. [source] Synthesis of Polyarylated Methanes through Cross-Coupling of Tricarbonylchromium-Activated Benzyllithiums,ANGEWANDTE CHEMIE, Issue 32 2010Genette Hilfsgruppe: Im Komplex mit dem Tricarbonylchrom-Fragment gehen typischerweise instabile Benzyllithium-Reagentien direkt Kreuzkupplungen mit Arylbromiden unter Bildung von Polyarylmethanen ein (siehe Schema). Die Cr(CO)3 -Gruppe macht viele koordinierte Substrate reaktiv und ermöglicht , je nach der Zahl vorhandener Benzylpositionen , bis zu sechs Kupplungsereignisse pro Aren. TMS=Trimethylsilyl. [source] ChemInform Abstract: Synthesis of Methanes Having Four Different Carbon Substituents Utilizing Indium-Catalyzed Cleavage of Carbon,Pyrrolyl Bonds.CHEMINFORM, Issue 37 2009Teruhisa Tsuchimoto Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] Zeolite Catalyzed Synthesis of Bis(indolyl) Methanes.CHEMINFORM, Issue 8 2004A. Vijender Reddy No abstract is available for this article. [source] Native wildlife on rangelands to minimize methane and produce lower-emission meat: kangaroos versus livestockCONSERVATION LETTERS, Issue 3 2008George R. Wilson Abstract Ruminant livestock produce the greenhouse gas methane and so contribute to global warming and biodiversity reduction. Methane from the foregut of cattle and sheep constitutes 11% of Australia's total greenhouse gas emissions (GHG). Kangaroos, on the other hand, are nonruminant forestomach fermenters that produce negligible amounts of methane. We quantified the GHG savings Australia could make if livestock were reduced on the rangelands where kangaroo harvesting occurs and kangaroo numbers increased to 175 million to produce same amount of meat. Removing 7 million cattle and 36 million sheep by 2020 would lower Australia's GHG emissions by 16 megatonnes, or 3% of Australia's annual emissions. However, the change will require large cultural and social adjustments and reinvestment. Trials are underway based on international experiences of managing free-ranging species. They are enabling collaboration between farmers, and if they also show benefits to sustainability, rural productivity, and conservation of biodiversity, they could be expanded to incorporate change on the scale of this article. Farmers have few options to reduce the contribution that livestock make to GHG production. Using kangaroos to produce low-emission meat is an option for the Australian rangelands which would avoid permit fees under Australia's Emissions Trading Scheme, and could even have global application. [source] Metagenome and mRNA expression analyses of anaerobic methanotrophic archaea of the ANME-1 groupENVIRONMENTAL MICROBIOLOGY, Issue 2 2010Anke Meyerdierks Summary Microbial consortia mediating the anaerobic oxidation of methane with sulfate are composed of methanotrophic Archaea (ANME) and Bacteria related to sulfate-reducing Deltaproteobacteria. Cultured representatives are not available for any of the three ANME clades. Therefore, a metagenomic approach was applied to assess the genetic potential of ANME-1 archaea. In total, 3.4 Mbp sequence information was generated based on metagenomic fosmid libraries constructed directly from a methanotrophic microbial mat in the Black Sea. These sequence data represent, in 30 contigs, about 82,90% of a composite ANME-1 genome. The dataset supports the hypothesis of a reversal of the methanogenesis pathway. Indications for an assimilatory, but not for a dissimilatory sulfate reduction pathway in ANME-1, were found. Draft genome and expression analyses are consistent with acetate and formate as putative electron shuttles. Moreover, the dataset points towards downstream electron-accepting redox components different from the ones known from methanogenic archaea. Whereas catalytic subunits of [NiFe]-hydrogenases are lacking in the dataset, genes for an [FeFe]-hydrogenase homologue were identified, not yet described to be present in methanogenic archaea. Clustered genes annotated as secreted multiheme c -type cytochromes were identified, which have not yet been correlated with methanogenesis-related steps. The genes were shown to be expressed, suggesting direct electron transfer as an additional possible mode to shuttle electrons from ANME-1 to the bacterial sulfate-reducing partner. [source] Characterization of marine isoprene-degrading communitiesENVIRONMENTAL MICROBIOLOGY, Issue 12 2009Laura Acuña Alvarez Summary Isoprene is a volatile and climate-altering hydrocarbon with an atmospheric concentration similar to that of methane. It is well established that marine algae produce isoprene; however, until now there was no specific information about marine isoprene sinks. Here we demonstrate isoprene consumption in samples from temperate and tropical marine and coastal environments, and furthermore show that the most rapid degradation of isoprene coincides with the highest rates of isoprene production in estuarine sediments. Isoprene-degrading enrichment cultures, analysed by denaturing gradient gel electrophoresis and 454 pyrosequencing of the 16S rRNA gene and by culturing, were generally dominated by Actinobacteria, but included other groups such as Alphaproteobacteria and Bacteroidetes, previously not known to degrade isoprene. In contrast to specialist methane-oxidizing bacteria, cultivated isoprene degraders were nutritionally versatile, and nearly all of them were able to use n -alkanes as a source of carbon and energy. We therefore tested and showed that the ubiquitous marine hydrocarbon-degrader, Alcanivorax borkumensis, could also degrade isoprene. A mixture of the isolates consumed isoprene emitted from algal cultures, confirming that isoprene can be metabolized at low, environmentally relevant concentrations, and suggesting that, in the absence of spilled petroleum hydrocarbons, algal production of isoprene could maintain viable populations of hydrocarbon-degrading microbes. This discovery of a missing marine sink for isoprene is the first step in obtaining more robust predictions of its flux, and suggests that algal-derived isoprene provides an additional source of carbon for diverse microbes in the oceans. [source] In situ measurement of methane fluxes and analysis of transcribed particulate methane monooxygenase in desert soilsENVIRONMENTAL MICROBIOLOGY, Issue 10 2009Roey Angel Summary Aerated soils are a biological sink for atmospheric methane. However, the activity of desert soils and the presence of methanotrophs in these soils have hardly been studied. We studied on-site atmospheric methane consumption rates as well as the diversity and expression of the pmoA gene, coding for a subunit of the particulate methane monooxygenase, in arid and hyperarid soils in the Negev Desert, Israel. Methane uptake was only detected in undisturbed soils in the arid region (,90 mm year,1) and vertical methane profiles in soil showed the active layer to be at 0,20 cm depth. No methane uptake was detected in the hyperarid soils (,20 mm year,1) as well as in disturbed soils in the arid region (i.e. agricultural field and a mini-catchment). Molecular analysis of the methanotrophic community using terminal restriction fragment length polymorphism (T-RFLP) and cloning/sequencing of the pmoA gene detected methanotrophs in the active soils, whereas the inactive ones were dominated by sequences of the homologous gene amoA, coding for a subunit of the ammonia monooxygenase. Even in the active soils, methanotrophs (as well as in situ activity) could not be detected in the soil crust, which is the biologically most important layer in desert soils. All pmoA sequences belonged to yet uncultured strains. Transcript analysis showed dominance of sequences clustering within the JR3, formerly identified in Californian grassland soils. Our results show that although active methanotrophs are prevalent in arid soils they seem to be absent or inactive in hyperarid and disturbed arid soils. Furthermore, we postulate that methanotrophs of the yet uncultured JR3 cluster are the dominant atmospheric methane oxidizers in this ecosystem. [source] Denitrifying bacteria anaerobically oxidize methane in the absence of ArchaeaENVIRONMENTAL MICROBIOLOGY, Issue 11 2008Katharina F. Ettwig Summary Recently, a microbial consortium was shown to couple the anaerobic oxidation of methane to denitrification, predominantly in the form of nitrite reduction to dinitrogen gas. This consortium was dominated by bacteria of an as yet uncharacterized division and archaea of the order Methanosarcinales. The present manuscript reports on the upscaling of the enrichment culture, and addresses the role of the archaea in methane oxidation. The key gene of methanotrophic and methanogenic archaea, mcrA, was sequenced. The associated cofactor F430 was shown to have a mass of 905 Da, the same as for methanogens and different from the heavier form (951 Da) found in methanotrophic archaea. After prolonged enrichment (> 1 year), no inhibition of anaerobic methane oxidation was observed in the presence of 20 mM bromoethane sulfonate, a specific inhibitor of MCR. Optimization of the cultivation conditions led to higher rates of methane oxidation and to the decline of the archaeal population, as shown by fluorescence in situ hybridization and quantitative MALDI-TOF analysis of F430. Mass balancing showed that methane oxidation was still coupled to nitrite reduction in the total absence of oxygen. Together, our results show that bacteria can couple the anaerobic oxidation of methane to denitrification without the involvement of Archaea. [source] | |||||||||||||||||||||||||||||||||||||||||||