CH4 concentrations and fluxes in a subtropical metropolitan river network: Watershed urbanization impacts and environmental controls.

PubMed

Wang, Xiaofeng; He, Yixin; Chen, Huai; Yuan, Xingzhong; Peng, Changhui; Yue, Junsheng; Zhang, Qiaoyong; Zhou, Lilei

2018-05-01

Urbanization and greenhouse gas emissions are of great global concern, especially in developing countries such as China. However, little is known about the relationship between the two. In this study, we examined the influences of the urbanization of Chongqing Municipality, which covers an area of 5494km 2 , in China, on the CH 4 emissions of in its metropolitan river network. The results from 84 sampling locations showed an overall mean CH 4 concentration of 0.69±1.37μmol·L -1 and a CH 4 flux from the river network of 1.40±2.53mmolCH 4 m -2 d -1 . The CH 4 concentrations and fluxes presented a clear seasonal pattern, with the highest value in the spring and the lowest in the summer. Such seasonal variations were probably co-regulated by the dilution effect, temperature and supply of fresh organic matter by algal blooms. Another important result was that the CH 4 concentrations and fluxes increased with the degree of urbanization or the proportion of urban land use, being approximately 3-13 times higher in urban and suburban areas than in rural ones. The total nitrogen, dissolved oxygen (O%) and possible sewage discharge, which could affect the in situ CH 4 production and exogenous CH 4 input respectively, were important factors that influenced the spatial patterns of CH 4 in human-dominated river networks, while the nitrogen (N) and phosphorus (P) could be good predictors of the CH 4 emissions in urban watersheds. Hydrologic drivers, including bottom sediment type, flow velocity and river width, were strongly correlated with the CH 4 concentrations and could also affect the spatial variance and predict the CH 4 hotspots in such metropolitan river networks. With increasing urbanization, we should pay more attention to the increasing greenhouse gas emissions associated with urbanization. Copyright © 2017 Elsevier B.V. All rights reserved.

Low-Concentration Kinetics of Atmospheric CH4 Oxidation in Soil and Mechanism of NH4+ Inhibition

PubMed Central

Gulledge, Jay; Schimel, Joshua P.

1998-01-01

NH4+ inhibition kinetics for CH4 oxidation were examined at near-atmospheric CH4 concentrations in three upland forest soils. Whether NH4+-independent salt effects could be neutralized by adding nonammoniacal salts to control samples in lieu of deionized water was also investigated. Because the levels of exchangeable endogenous NH4+ were very low in the three soils, desorption of endogenous NH4+ was not a significant factor in this study. The Km(app) values for water-treated controls were 9.8, 22, and 57 nM for temperate pine, temperate hardwood, and birch taiga soils, respectively. At CH4 concentrations of ≤15 μl liter−1, oxidation followed first-order kinetics in the fine-textured taiga soil, whereas the coarse-textured temperate soils exhibited Michaelis-Menten kinetics. Compared to water controls, the Km(app) values in the temperate soils increased in the presence of NH4+ salts, whereas the Vmax(app) values decreased substantially, indicating that there was a mixture of competitive and noncompetitive inhibition mechanisms for whole NH4+ salts. Compared to the corresponding K+ salt controls, the Km(app) values for NH4+ salts increased substantially, whereas the Vmax(app) values remained virtually unchanged, indicating that NH4+ acted by competitive inhibition. Nonammoniacal salts caused inhibition to increase with increasing CH4 concentrations in all three soils. In the birch taiga soil, this trend occurred with both NH4+ and K+ salts, and the slope of the increase was not affected by the addition of NH4+. Hence, the increase in inhibition resulted from an NH4+-independent mechanism. These results show that NH4+ inhibition of atmospheric CH4 oxidation resulted from enzymatic substrate competition and that additional inhibition that was not competitive resulted from a general salt effect that was independent of NH4+. PMID:9797279

Landscape patterns of CH4 fluxes in an alpine tundra ecosystem

USGS Publications Warehouse

West, A.E.; Brooks, P.D.; Fisk, M.C.; Smith, Lesley K.; Holland, E.A.; Jaeger, C. H.; Babcock, S.; Lai, R.S.; Schmidt, S.K.

1999-01-01

We measured CH4 fluxes from three major plant communities characteristic of alpine tundra in the Colorado Front Range. Plant communities in this ecosystem are determined by soil moisture regimes induced by winter snowpack distribution. Spatial patterns of CH4 flux during the snow-free season corresponded roughly with these plant communities. In Carex-dominated meadows, which receive the most moisture from snowmelt, net CH4 production occurred. However, CH4 production in one Carex site (seasonal mean = +8.45 mg CH4 m-2 d-1) was significantly larger than in the other Carex sites (seasonal means = -0.06 and +0.05 mg CH4 m-2 d-1). This high CH4 flux may have resulted from shallower snowpack during the winter. In Acomastylis meadows, which have an intermediate moisture regime, CH4 oxidation dominated (seasonal mean = -0.43 mg CH4 m-2 d-1). In the windswept Kobresia meadow plant community, which receive the least amount of moisture from snowmelt, only CH4 oxidation was observed (seasonal mean = -0.77 mg CH4 m-2 d-1). Methane fluxes correlated with a different set of environmental factors within each plant community. In the Carex plant community, CH4 emission was limited by soil temperature. In the Acomastylis meadows, CH4 oxidation rates correlated positively with soil temperature and negatively with soil moisture. In the Kobresia community, CH4 oxidation was stimulated by precipitation. Thus, both snow-free season CH4 fluxes and the controls on those CH4 fluxes were related to the plant communities determined by winter snowpack.

The Drivers of the CH4 Seasonal Cycle in the Arctic and What Long-Term Observations of CH4 Imply About Trends in Arctic CH4 Fluxes

NASA Astrophysics Data System (ADS)

Sweeney, C.; Karion, A.; Bruhwiler, L.; Miller, J. B.; Wofsy, S. C.; Miller, C. E.; Chang, R. Y.; Dlugokencky, E. J.; Daube, B.; Pittman, J. V.; Dinardo, S. J.

2012-12-01

The large seasonal change in the atmospheric column for CH4 in the Arctic is driven by two dominant processes: transport of CH4 from low latitudes and surface emissions throughout the Arctic region. The NOAA ESRL Carbon Cycle Group Aircraft Program along with the NASA funded Carbon in Arctic Reservoirs Vulnerability Experiment (CARVE) have initiated an effort to better understand the factors controlling the seasonal changes in the mole fraction of CH4 in the Arctic with a multi-scale aircraft observing network in Alaska. The backbone of this network is multi-species flask sampling from 500 to 8000 masl that has been conducted every two weeks for the last 10 years over Poker Flat, AK. In addition regular profiles at the interior Alaska site at Poker Flat, NOAA has teamed up with the United States Coast Guard to make profiling flights with continuous observations of CO2, CO, CH4 and Ozone between Kodiak and Barrow every 2 weeks. More recently, CARVE has significantly added to this observational network with targeted flights focused on exploring the variability of CO2, CH4 and CO in the boundary layer both in the interior and the North Slope regions of Alaska. Taken together with the profiling of HIAPER Pole-to-Pole Observations (HIPPO), ground sites at Barrow and a new CARVE interior Alaska surface site just north of Fairbanks, AK, we now have the ability to investigate the full evolution of the seasonal cycle in the Arctic using both the multi-scale sampling offered by the different aircraft platforms as well as the multi-species sampling offered by in-situ and flask sampling. The flasks also provide a valuable tie-point between different platforms so that spatial and temporal gradients can be properly interpreted. In the context of the seasonal cycle observed by the aircraft platforms we will look at long term ground observations over the last 20 years to assess changes in Arctic CH4 emissions which have occurred as a result of 0.6C/decade changes in mean surface

Unusual reaction paths of SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-: Quantum chemical calculations

NASA Astrophysics Data System (ADS)

Minyaev, Ruslan M.; Quapp, Wolfgang; Schmidt, Benjamin; Getmanskii, Ilya V.; Koval, Vitaliy V.

2013-11-01

Quantum chemical (CCSD(full)/6-311++G(3df,3pd), CCSD(T)(full)/6-311++G(3df,3pd)) and density function theory (B3LYP/6-311++G(3df,3pd)) calculations were performed for the SN2 nucleophile substitution reactions CH4 + H- → CH4 + H- and CH4 + F- → CH3F + H-. The calculated gradient reaction pathways for both reactions have an unusual behavior. An unusual stationary point of index 2 lies on the gradient reaction path. Using Newton trajectories for the reaction path, we can detect VRI point at which the reaction path branches.

Martian CH(4): sources, flux, and detection.

PubMed

Onstott, T C; McGown, D; Kessler, J; Lollar, B Sherwood; Lehmann, K K; Clifford, S M

2006-04-01

Recent observations have detected trace amounts of CH(4) heterogeneously distributed in the martian atmosphere, which indicated a subsurface CH(4) flux of ~2 x 10(5) to 2 x 10(9) cm(2) s(1). Four different origins for this CH(4) were considered: (1) volcanogenic; (2) sublimation of hydrate- rich ice; (3) diffusive transport through hydrate-saturated cryosphere; and (4) microbial CH(4) generation above the cryosphere. A diffusive flux model of the martian crust for He, H(2), and CH(4) was developed based upon measurements of deep fracture water samples from South Africa. This model distinguishes between abiogenic and microbial CH(4) sources based upon their isotopic composition, and couples microbial CH(4) production to H(2) generation by H(2)O radiolysis. For a He flux of approximately 10(5) cm(2) s(1) this model yields an abiogenic CH(4) flux and a microbial CH(4) flux of approximately 10(6) and approximately 10(9) cm(2) s(1), respectively. This flux will only reach the martian surface if CH(4) hydrate is saturated in the cryosphere; otherwise it will be captured within the cryosphere. The sublimation of a hydrate-rich cryosphere could generate the observed CH(4) flux, whereas microbial CH(4) production in a hypersaline environment above the hydrate stability zone only seems capable of supplying approximately 10(5) cm(2) s(1) of CH(4). The model predicts that He/H(2)/CH(4)/C(2)H(6) abundances and the C and H isotopic values of CH(4) and the C isotopic composition of C(2)H(6) could reveal the different sources. Cavity ring-down spectrometers represent the instrument type that would be most capable of performing the C and H measurements of CH(4) on near future rover missions and pinpointing the cause and source of the CH(4) emissions.

Aviation NOx-induced CH4 effect: Fixed mixing ratio boundary conditions versus flux boundary conditions

NASA Astrophysics Data System (ADS)

Khodayari, Arezoo; Olsen, Seth C.; Wuebbles, Donald J.; Phoenix, Daniel B.

2015-07-01

Atmospheric chemistry-climate models are often used to calculate the effect of aviation NOx emissions on atmospheric ozone (O3) and methane (CH4). Due to the long (∼10 yr) atmospheric lifetime of methane, model simulations must be run for long time periods, typically for more than 40 simulation years, to reach steady-state if using CH4 emission fluxes. Because of the computational expense of such long runs, studies have traditionally used specified CH4 mixing ratio lower boundary conditions (BCs) and then applied a simple parameterization based on the change in CH4 lifetime between the control and NOx-perturbed simulations to estimate the change in CH4 concentration induced by NOx emissions. In this parameterization a feedback factor (typically a value of 1.4) is used to account for the feedback of CH4 concentrations on its lifetime. Modeling studies comparing simulations using CH4 surface fluxes and fixed mixing ratio BCs are used to examine the validity of this parameterization. The latest version of the Community Earth System Model (CESM), with the CAM5 atmospheric model, was used for this study. Aviation NOx emissions for 2006 were obtained from the AEDT (Aviation Environmental Design Tool) global commercial aircraft emissions. Results show a 31.4 ppb change in CH4 concentration when estimated using the parameterization and a 1.4 feedback factor, and a 28.9 ppb change when the concentration was directly calculated in the CH4 flux simulations. The model calculated value for CH4 feedback on its own lifetime agrees well with the 1.4 feedback factor. Systematic comparisons between the separate runs indicated that the parameterization technique overestimates the CH4 concentration by 8.6%. Therefore, it is concluded that the estimation technique is good to within ∼10% and decreases the computational requirements in our simulations by nearly a factor of 8.

CH_{4} production in the deep soil as a source of stem CH_{4} emission in Fagus sylvatica}

NASA Astrophysics Data System (ADS)

Maier, Martin; Machacova, Katerina; Urban, Otmar; Lang, Friederike

2017-04-01

Predicting greenhouse gas (GHG) fluxes on a global scale requires understanding fluxes on the local scale. Understanding GHG processes in soil-plant-atmosphere systems is essential to understand and mitigate GHG fluxes on the local scale. Forests are known to act as carbon sink. Yet, trees at waterlogged sites are known to emit large amounts of CH4, what can offset the positive GHG balance due the CO2 that is sequestered as wood. Generally, upland trees like European beech (Fagus sylvatica L.) are assumed not to emit CH4, and the upland forest soils are regarded as CH4 sinks. Soil-atmosphere fluxes and stem-atmosphere fluxes of CH4 were studied together with soil gas profiles at two upland beech forest sites in Germany and Czech Republic. Soil was a net CH4 sink at both sites. While most trees showed no or low emissions, one beech tree had exorbitant CH4 emissions that were higher than the CH4 sink capacity of the soil. A soil survey showed strong redoximorphic color patterns in the soil adjacent to this tree. Although the soil around the tree was taking up CH4, the soil gas profiles around this tree showed CH4 production at a soil depth >0.3 m. We interpret the coincidence of the production of CH4 in the deep soil below the beech with the large stem emissions as strong hint that there is a transport link between the soil and stem. We think that the root system represents a preferential transport system for CH4 despite the fact that beech roots usually do not have a special gas transport tissue. The observed CH4 stem emissions represent an important CH4 flux in this ecosystem, and, thus, should be considered in future research. Acknowledgement This research was supported by the Czech Academy of Sciences and the German Academic Exchange Service within the project "Methane (CH4) and nitrous oxide (N2O) emissions from Fagus sylvatica trees" (DAAD-15-03), the Czech Science Foundation (17-18112Y), National Programme for Sustainability I (LO1415) and project DFG (MA 5826

CH4 emissions from two floodplain fens of differing nutrient status

NASA Astrophysics Data System (ADS)

Stanley, Kieran; Heppell, Catherine; Belyea, Lisa; Baird, Andrew

2014-05-01

Floodplain fens emit large amounts of CH4 in comparison with ombrotrophic bogs. Little is known about the effect of fluvial nitrogen (N) and phosphorus (P) on CH4 dynamics in fens, although N and P affect carbon (C) dynamics indirectly in other environments by controlling plant growth and root exudate release, as well as by altering microbial biomass and decomposition rates. This study aimed to compare CH4 emissions from two floodplain fen sites which differ in nutrient status, Sutton Fen (52°45'N 001°30'E) and Strumpshaw Fen (52°36'N 001°27'E), in the Norfolk Broadland of England. Sutton and Strumpshaw Fen are under conservation management and both sites have water levels that vary within a few decimetres above and below the surface. The sites are dominated by reed (Phragmites australis). Areas within the fens where the reed was cut in 2009 were chosen for this study. Average plant height and mean aboveground biomass were significantly greater at Strumpshaw (107.2 ± 7.8 cm and 1578 ± 169 g m-2, respectively) than Sutton (56.5 ± 5.1 cm and 435 ± 42 g m-2) as were mean foliar N and P contents (21.8 ± 1.5 g kg-1 and 2.0 ± 0.2 g kg-1 at Strumpshaw, versus 16.3 ± 1.5 g kg-1 and 1.1 ± 0.1 g kg-1 at Sutton). Foliar NPK ratios showed Strumpshaw to be N limited, whereas Sutton was both N and P limited, depending on microsite. Surface peat N and P contents were also greater at Strumpshaw (28.3 ± 0.35 g kg-1 and 0.78 ± 0.02 g kg-1, respectively) than Sutton (18.32 ± 0.87 g kg-1 and 0.43 ± 0.1 g kg-1). These results indicate clear differences in nutrient status between the two sites despite their geographical proximity and other similarities. CH4 emissions were monitored monthly between 19th June 2012 and 2nd September 2013 using tall static chambers and glass funnel-traps, the latter for ebullition. Steady fluxes did not follow a clear seasonal pattern; however, emission was greatest in the summer months. Strumpshaw had a greater range in efflux (0.25 to 134

Distinct transport properties of O2 and CH4 across a carbon nanotube

NASA Astrophysics Data System (ADS)

Meng, Xianwen; Wang, Yu; Zhao, Yanjiao; Huang, Jiping

2013-04-01

It is of fundamental importance to investigate either O2 or CH4 molecules across nanochannels in many areas such as breathing or separation. Thus, many researches have focused on such a single type of molecules across nanochannels. However, O2 and CH4 can often appear together and crucially affect human life, say, in a mine. On the basis of molecular dynamics simulations, here we attempt to investigate the mixture of O2 and CH4, in order to identify their different transport properties in a nanochannel. We take a single-walled carbon nanotube (SWCNT) as a model nanochannel, and find that their transport properties are distinctly different. As the concentration of O2 increases up to a high value of 0.8, it is always faster for CH4 molecules to transport across the SWCNT, and the total number of gas molecules transporting across the SWCNT is decreased. Meanwhile, CH4 molecules are always dominant in the SWCNT, and the total number of O2 or CH4 inside the SWCNT is a constant. By calculating the van der Waals interaction between the SWCNT and O2 or CH4, we find that the net interaction between CH4 and the SWCNT is much stronger. Our findings may offer some hints on how to separate CH4 from O2, and/or store CH4 efficiently.

Using carbon isotope fractionation for an improved quantification of CH4 oxidation efficiency in Arctic peatlands

NASA Astrophysics Data System (ADS)

Preuss, I.; Knoblauch, C.; Gebert, J.; Pfeiffer, E.-M.

2012-04-01

Much research effort is focused on identifying global CH4 sources and sinks to estimate their current and potential strength in response to land-use change and global warming. Aerobic CH4 oxidation is regarded as the key process reducing the strength of CH4 emissions in wetlands, but is hitherto difficult to quantify. Recent studies quantify the efficiency of CH4 oxidation based on CH4 stable isotope signatures. The approach utilizes the fact that a significant isotope fractionation occurs when CH4 is oxidized. Moreover, it also considers isotope fractionation by diffusion. For field applications the 'open-system equation' is applied to determine the CH4 oxidation efficiency: fox = (δE - δP)/ (αox - αtrans) where fox is the fraction of CH4 oxidized; δE is δ13C of emitted CH4; δP is δ13C of produced CH4; αox is the isotopic fractionation factor of oxidation; αtrans is the isotopic fractionation factor of transport. We quantified CH4 oxidation in polygonal tundra soils of Russia's Lena River Delta analyzing depth profiles of CH4 concentrations and stable isotope signatures. Therefore, both fractionation factors αox and αtrans were determined for three polygon centers with differing water table positions and a polygon rim. While most previous studies on landfill cover soils have assumed a gas transport dominated by advection (αtrans = 1), other CH4 transport mechanisms as diffusion have to be considered in peatlands and αtrans exceeds a value of 1. At our study we determined αtrans = 1.013 ± 0.003 for CH4 when diffusion is the predominant transport mechanism. Furthermore, results showed that αox differs widely between sites and horizons (αox = 1.013 ± 0.012) and has to be determined for each case. The impact of both fractionation factors on the quantification of CH4 oxidation was estimated by considering both the potential diffusion rate at different water contents and potential oxidation rates. Calculations for a water saturated tundra soil

CH4 Hydrate Formation between Silica and Graphite Surfaces: Insights from Microsecond Molecular Dynamics Simulations.

PubMed

He, Zhongjin; Linga, Praveen; Jiang, Jianwen

2017-10-31

, as well as the ability of graphite to adsorb CH 4 molecules and induce hydrate-like ordering of the interfacial water, are the key factors to affect CH 4 hydrate formation between silica and graphite surfaces.

Ranking factors affecting emissions of GHG from incubated agricultural soils.

PubMed

García-Marco, S; Ravella, S R; Chadwick, D; Vallejo, A; Gregory, A S; Cárdenas, L M

2014-07-01

Agriculture significantly contributes to global greenhouse gas (GHG) emissions and there is a need to develop effective mitigation strategies. The efficacy of methods to reduce GHG fluxes from agricultural soils can be affected by a range of interacting management and environmental factors. Uniquely, we used the Taguchi experimental design methodology to rank the relative importance of six factors known to affect the emission of GHG from soil: nitrate (NO 3 - ) addition, carbon quality (labile and non-labile C), soil temperature, water-filled pore space (WFPS) and extent of soil compaction. Grassland soil was incubated in jars where selected factors, considered at two or three amounts within the experimental range, were combined in an orthogonal array to determine the importance and interactions between factors with a L 16 design, comprising 16 experimental units. Within this L 16 design, 216 combinations of the full factorial experimental design were represented. Headspace nitrous oxide (N 2 O), methane (CH 4 ) and carbon dioxide (CO 2 ) concentrations were measured and used to calculate fluxes. Results found for the relative influence of factors (WFPS and NO 3 - addition were the main factors affecting N 2 O fluxes, whilst glucose, NO 3 - and soil temperature were the main factors affecting CO 2 and CH 4 fluxes) were consistent with those already well documented. Interactions between factors were also studied and results showed that factors with little individual influence became more influential in combination. The proposed methodology offers new possibilities for GHG researchers to study interactions between influential factors and address the optimized sets of conditions to reduce GHG emissions in agro-ecosystems, while reducing the number of experimental units required compared with conventional experimental procedures that adjust one variable at a time.

Ranking factors affecting emissions of GHG from incubated agricultural soils

PubMed Central

García-Marco, S; Ravella, S R; Chadwick, D; Vallejo, A; Gregory, A S; Cárdenas, L M

2014-01-01

Agriculture significantly contributes to global greenhouse gas (GHG) emissions and there is a need to develop effective mitigation strategies. The efficacy of methods to reduce GHG fluxes from agricultural soils can be affected by a range of interacting management and environmental factors. Uniquely, we used the Taguchi experimental design methodology to rank the relative importance of six factors known to affect the emission of GHG from soil: nitrate (NO3−) addition, carbon quality (labile and non-labile C), soil temperature, water-filled pore space (WFPS) and extent of soil compaction. Grassland soil was incubated in jars where selected factors, considered at two or three amounts within the experimental range, were combined in an orthogonal array to determine the importance and interactions between factors with a L16 design, comprising 16 experimental units. Within this L16 design, 216 combinations of the full factorial experimental design were represented. Headspace nitrous oxide (N2O), methane (CH4) and carbon dioxide (CO2) concentrations were measured and used to calculate fluxes. Results found for the relative influence of factors (WFPS and NO3− addition were the main factors affecting N2O fluxes, whilst glucose, NO3− and soil temperature were the main factors affecting CO2 and CH4 fluxes) were consistent with those already well documented. Interactions between factors were also studied and results showed that factors with little individual influence became more influential in combination. The proposed methodology offers new possibilities for GHG researchers to study interactions between influential factors and address the optimized sets of conditions to reduce GHG emissions in agro-ecosystems, while reducing the number of experimental units required compared with conventional experimental procedures that adjust one variable at a time. PMID:25177207

Effects of shifting growth stage and regulating temperature on seasonal variation of CH4 emission from rice

NASA Astrophysics Data System (ADS)

Watanabe, Akira; Yamada, Hiromi; Kimura, Makoto

2001-09-01

Seasonal variations in CH4 emission rates from rice paddies have been reported to have one or more maxima during the middle and late periods of rice growth. The factor affecting an appearance of CH4 emission maxima was examined in three types of pot experiments. In the experiment 1, four rice cultivars with difference in length of the period from transplanting to heading were transplanted on the same days. For the experiment 2, a cultivar was transplanted 4 times with interval of two weeks. In these experiments, the heading differed about a month between the earliest and latest treatments, respectively. However, shifting growth stage of rice plants did not shift the CH4 emission maxima, and the CH4 emission maxima often matched the maxima of daily mean air temperature. The effect of variation in temperature on CH4 emission rate was further investigated in the experiment 3 by placing the rice-planted pots under regulated temperature. Besides the first emission peak of CH4 attributable to rice straw (RS) carbon, three emission peaks corresponding to the peaks of air temperature were detected for the RS-applied pots placed outdoors. These three peaks were not observed or much less conspicuous for the RS-applied pots in a phytotron at 30°C. Temporal decreases in CH4 emission were detected both for the pots placed in the phytotron and outdoors just after the topdressing of (NH4)2SO4, which was considered to be a major cause of irregular disagreement between the variations in CH4 emission rates and in air temperature during the middle period of rice growth.

Effects of Different Vegetation Zones on CH4 and N2O Emissions in Coastal Wetlands: A Model Case Study

PubMed Central

Liu, Yuhong; Wang, Lixin; Bao, Shumei; Liu, Huamin; Yu, Junbao; Wang, Yu; Shao, Hongbo; Ouyang, Yan; An, Shuqing

2014-01-01

The coastal wetland ecosystems are important in the global carbon and nitrogen cycle and global climate change. For higher fragility of coastal wetlands induced by human activities, the roles of coastal wetland ecosystems in CH4 and N2O emissions are becoming more important. This study used a DNDC model to simulate current and future CH4 and N2O emissions of coastal wetlands in four sites along the latitude in China. The simulation results showed that different vegetation zones, including bare beach, Spartina beach, and Phragmites beach, produced different emissions of CH4 and N2O in the same latitude region. Correlation analysis indicated that vegetation types, water level, temperature, and soil organic carbon content are the main factors affecting emissions of CH4 and N2O in coastal wetlands. PMID:24892044

A high level computational study of the CH4/CF4 dimer: how does it compare with the CH4/CH4 and CF4/CF4 dimers?

NASA Astrophysics Data System (ADS)

Biller, Matthew J.; Mecozzi, Sandro

2012-04-01

The interaction within the methane-methane (CH4/CH4), perfluoromethane-perfluoromethane (CF4/CF4) methane-perfluoromethane dimers (CH4/CF4) was calculated using the Hartree-Fock (HF) method, multiple orders of Møller-Plesset perturbation theory [MP2, MP3, MP4(DQ), MP4(SDQ), MP4(SDTQ)], and coupled cluster theory [CCSD, CCSD(T)], as well as the PW91, B97D, and M06-2X density functional theory (DFT) functionals. The basis sets of Dunning and coworkers (aug-cc-pVxZ, x = D, T, Q), Krishnan and coworkers [6-311++G(d,p), 6-311++G(2d,2p)], and Tsuzuki and coworkers [aug(df, pd)-6-311G(d,p)] were used. Basis set superposition error (BSSE) was corrected via the counterpoise method in all cases. Interaction energies obtained with the MP2 method do not fit with the experimental finding that the methane-perfluoromethane system phase separates at 94.5 K. It was not until the CCSD(T) method was considered that the interaction energy of the methane-perfluoromethane dimer (-0.69 kcal mol-1) was found to be intermediate between the methane (-0.51 kcal mol-1) and perfluoromethane (-0.78 kcal mol-1) dimers. This suggests that a perfluoromethane molecule interacts preferentially with another perfluoromethane (by about 0.09 kcal mol-1) than with a methane molecule. At temperatures much lower than the CH4/CF4 critical solution temperature of 94.5 K, this energy difference becomes significant and leads perfluoromethane molecules to associate with themselves, forming a phase separation. The DFT functionals yielded erratic results for the three dimers. Further development of DFT is needed in order to model dispersion interactions in hydrocarbon/perfluorocarbon systems.

Large-scale patterns in summer diffusive CH4 fluxes across boreal lakes, and contribution to diffusive C emissions.

PubMed

Rasilo, Terhi; Prairie, Yves T; Del Giorgio, Paul A

2015-03-01

Lakes are a major component of boreal landscapes, and whereas lake CO2 emissions are recognized as a major component of regional C budgets, there is still much uncertainty associated to lake CH4 fluxes. Here, we present a large-scale study of the magnitude and regulation of boreal lake summer diffusive CH4 fluxes, and their contribution to total lake carbon (C) emissions, based on in situ measurements of concentration and fluxes of CH4 and CO2 in 224 lakes across a wide range of lake type and environmental gradients in Québec. The diffusive CH4 flux was highly variable (mean 11.6 ± 26.4 SD mg m(-2)  d(-1) ), and it was positively correlated with temperature and lake nutrient status, and negatively correlated with lake area and colored dissolved organic matter (CDOM). The relationship between CH4 and CO2 concentrations fluxes was weak, suggesting major differences in their respective sources and/or regulation. For example, increasing water temperature leads to higher CH4 flux but does not significantly affect CO2 flux, whereas increasing CDOM concentration leads to higher CO2 flux but lower CH4 flux. CH4 contributed to 8 ± 23% to the total lake C emissions (CH4  + CO2 ), but 18 ± 25% to the total flux in terms of atmospheric warming potential, expressed as CO2 -equivalents. The incorporation of ebullition and plant-mediated CH4 fluxes would further increase the importance of lake CH4 . The average Q10 of CH4 flux was 3.7, once other covarying factors were accounted for, but this apparent Q10 varied with lake morphometry and was higher for shallow lakes. We conclude that global climate change and the resulting shifts in temperature will strongly influence lake CH4 fluxes across the boreal biome, but these climate effects may be altered by regional patterns in lake morphometry, nutrient status, and browning. © 2014 John Wiley & Sons Ltd.

Large CH4 production fueled by autochthonous OC in an anoxic sediment

NASA Astrophysics Data System (ADS)

Grasset, Charlotte; Mendonça, Raquel; Villamor Saucedo, Gabriella; Sobek, Sebastian

2017-04-01

River damming and human-induced eutrophication both affect river and lake functioning, increase organic carbon (OC) sedimentation rates and generate anoxic conditions in bottom waters. Under these conditions, OC in sediments is decomposed into CO2 and CH4, a high potential greenhouse gas. It has been shown that the decomposition of land-derived (allochthonous) OC is inhibited at anoxic conditions, compared to OC internally produced (autochthonous). However, the overall extent and end products (CO2 or CH4) of anoxic decomposition remain poorly known for different types of OC, making it difficult to judge the effect of river damming and eutrophication on greenhouse gas emissions from inland waters. We incubated different types of allochthonous OC (terrestrial plants) and autochthonous OC (phytoplankton and aquatic vascular plants) in an anoxic sediment during 130 days. We aimed to test 1) if this addition of relatively fresh OC resulted in an increase of CH4 production and 2) if autochthonous OC would produce more CH4 than allochthonous OC. We assessed the contribution to CH4 production of the different OC sources (i.e. sediment or added OC) with stable isotope measurements. We found that the addition of relatively fresh OC greatly increased CH4 production. Autochthonous OC generally produced more CH4 than allochthonous OC, but the overall extent of CH4 production was highly variable between the different autochthonous OC types. The d13C-CH4 measurements indicated that CH4 originated exclusively from the added OC. We conclude that the production of CH4 is likely to to be high in eutrophic as well as in artificial lakes, especially when these systems have anoxic bottom waters and high internal primary productivity and thus a high supply of autochthonous OC to the sediment. The current expansion of reservoir construction in concert with almost globally prevalent anthropogenic eutrophication are therefore likely to increase CH4 production in inland waters.

Luminescent Copper(I) Halide Butterfly Dimers Coordinated to [Au(CH3imCH2py)2]BF4 and [Au(CH3imCH2quin)2]BF4

DOE Office of Scientific and Technical Information (OSTI.GOV)

Catalano, V.; Moore, A; Shearer, J

2009-01-01

The coordination chemistry of copper(I) halides to the homoleptic, N-heterocyclic carbene Au(I) complexes [Au(CH{sub 3}imCH{sub 2}quin){sub 2}]BF{sub 4} and [Au(CH{sub 3}imCH{sub 2}py){sub 2}]BF{sub 4} was explored. The reaction of CuX (X = Cl, Br, I) with either [Au(CH{sub 3}imCH{sub 2}quin){sub 2}]BF{sub 4} or [Au(CH{sub 3}imCH{sub 2}py){sub 2}]BF{sub 4} produces trimetallic complexes containing Cu{sub 2}X{sub 2}-butterfly copper clusters coordinated to the two imine moieties. The triangular arrangement of the metals places the gold(I) center in close proximity ({approx}2.5-2.6 {angstrom}) to the centroid of the Cu-Cu vector. The Cu-Cu separations vary as a function of bridging halide with the shortest Cu-Cu separationsmore » of {approx}2.5 {angstrom} found in the iodo-complexes and the longest separations of 2.9 {angstrom} found in the bridging chloride complexes. In all six complexes the Au-Cu separations range from {approx}2.8 to 3.0 {angstrom}. In the absence of halides, the dimetallic complex [AuCu(CH{sub 3}imCH{sub 2}py){sub 2}(NCCH{sub 3}){sub 2}](BF{sub 4}){sub 2}, containing a long Au-Cu distance of {approx}4.72 {angstrom} is formed. Additionally, as the byproduct of the reaction of CuBr with [Au(CH{sub 3}imCH{sub 2}quin){sub 2}]BF{sub 4} the deep-red, dimetallic compound, AuCuBr{sub 2}(CH{sub 3}imCH{sub 2}quin){sub 2}, was isolated in very low yield. All of these complexes were studied by NMR spectroscopy, mass spectrometry, and the copper containing species were additionally characterized by X-ray crystallography. In solution the copper centers dissociate from the gold complexes, but as shown by XANES and EXAFS spectroscopy, at low temperature the Cu-Cu linkage is broken, and the individual copper(I) halides reposition themselves to opposite sides of the gold complex while remaining coordinated to one imine moiety. In the solid state all of the complexes are photoluminescent, though the nature of the excited state was not determined.« less

Degraded Land Restoration in Reinstating CH4 Sink

PubMed Central

Singh, Jay Shankar; Gupta, Vijai K.

2016-01-01

Methane (CH4), a potent greenhouse gas, contributes about one third to the global green house gas emissions. CH4-assimilating microbes (mostly methanotrophs) in upland soils play very crucial role in mitigating the CH4 release into the atmosphere. Agricultural, environmental, and climatic shifts can alter CH4 sink profiles of soils, likely through shifts in CH4-assimilating microbial community structure and function. Landuse change, as forest and grassland ecosystems altered to agro-ecosystems, has already attenuated the soil CH4 sink potential, and are expected to be continued in the future. We hypothesized that variations in CH4 uptake rates in soils under different landuse practices could be an indicative of alterations in the abundance and/or type of methanotrophic communities in such soils. However, only a few studies have addressed to number and methanotrophs diversity and their correlation with the CH4 sink potential in soils of rehabilitated/restored lands. We focus on landuse practices that can potentially mitigate CH4 gas emissions, the most prominent of which are improved cropland, grazing land management, use of bio-fertilizers, and restoration of degraded lands. In this perspective paper, it is proposed that restoration of degraded lands can contribute considerably to improved soil CH4 sink strength by retrieving/conserving abundance and assortment of efficient methanotrophic communities. We believe that this report can assist in identifying future experimental directions to the relationships between landuse changes, methane-assimilating microbial communities and soil CH4 sinks. The exploitation of microbial communities other than methanotrophs can contribute significantly to the global CH4 sink potential and can add value in mitigating the CH4 problems. PMID:27379053

Degraded Land Restoration in Reinstating CH4 Sink.

PubMed

Singh, Jay Shankar; Gupta, Vijai K

2016-01-01

Methane (CH4), a potent greenhouse gas, contributes about one third to the global green house gas emissions. CH4-assimilating microbes (mostly methanotrophs) in upland soils play very crucial role in mitigating the CH4 release into the atmosphere. Agricultural, environmental, and climatic shifts can alter CH4 sink profiles of soils, likely through shifts in CH4-assimilating microbial community structure and function. Landuse change, as forest and grassland ecosystems altered to agro-ecosystems, has already attenuated the soil CH4 sink potential, and are expected to be continued in the future. We hypothesized that variations in CH4 uptake rates in soils under different landuse practices could be an indicative of alterations in the abundance and/or type of methanotrophic communities in such soils. However, only a few studies have addressed to number and methanotrophs diversity and their correlation with the CH4 sink potential in soils of rehabilitated/restored lands. We focus on landuse practices that can potentially mitigate CH4 gas emissions, the most prominent of which are improved cropland, grazing land management, use of bio-fertilizers, and restoration of degraded lands. In this perspective paper, it is proposed that restoration of degraded lands can contribute considerably to improved soil CH4 sink strength by retrieving/conserving abundance and assortment of efficient methanotrophic communities. We believe that this report can assist in identifying future experimental directions to the relationships between landuse changes, methane-assimilating microbial communities and soil CH4 sinks. The exploitation of microbial communities other than methanotrophs can contribute significantly to the global CH4 sink potential and can add value in mitigating the CH4 problems.

Analysis of the heat capacity for pure CH4 and CH4/CCl4 on graphite near the melting point and calculation of the T-X phase diagram for (CH3)CCl3 + CCl4

NASA Astrophysics Data System (ADS)

Yurtseven, Hamit; Yılmaz, Aygül

2016-06-01

We study the temperature dependence of the heat capacity Cp for the pure CH4 and the coadsorbed CH4/CCl4 on graphite near the melting point. The heat capacity peaks are analyzed using the experimental data from the literature by means of the power-law formula. The critical exponents for the heat capacity are deduced below and above the melting point for CH4 (Tm = 104.8 K) and CH4/CCl4 (Tm = 99.2 K). Our exponent values are larger as compared with the predicted values of some theoretical models exhibiting second order transition. Our analyses indicate that the pure methane shows a nearly second order (weak discontinuity in the heat capacity peak), whereas the transition in coadsorbed CH4/CCl4 is of first order (apparent discontinuity in Cp). We also study the T - X phase diagram of a two-component system of CH3CCl3+CCl4 using the Landau phenomenological model. Phase lines of the R+L (rhombohedral+liquid) and FCC+L (face-centred cubic + liquid) are calculated using the observed T - X phase diagram of this binary mixture. Our results show that the Landau mean field theory describes the observed behavior of CH3CCl3+CCl4 adequately. From the calculated T - X phase diagram, critical behavior of some thermodynamic quantities can be predicted at various temperatures and concentrations (CCl4) for a binary mixture of CH3CCl3+CCl4.

40 CFR Table Aa-2 to Subpart Aa of... - Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O AA Table AA-2 to Subpart AA of Part 98 Protection of Environment... and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O Fuel Fossil fuel-based emissions...

40 CFR Table Aa-2 to Subpart Aa of... - Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O AA Table AA-2 to Subpart AA of Part 98 Protection of Environment... and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O Fuel Fossil fuel-based emissions...

40 CFR Table Aa-2 to Subpart Aa of... - Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Kraft Lime Kiln and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O AA Table AA-2 to Subpart AA of Part 98 Protection of Environment... and Calciner Emissions Factors for Fossil Fuel-Based CH4 and N2O Fuel Fossil fuel-based emissions...

Inverse Modeling of Surface CH4 and δ13C-CH4 Measurements to Understand Recent Trends in Global Methane Emissions

NASA Astrophysics Data System (ADS)

Karmakar, S.; Butenhoff, C. L.; Rice, A. L.; Lofdahl, D. B.; Khalil, A. K.

2016-12-01

Methane (CH4) is the second most important greenhouse gas with a radiative forcing of 0.97 W/m2 including both direct and indirect effects and a global warming potential of 28 over a 100-year time horizon. Unlike CO2 whose rate of growth in the atmosphere has remained positive and increased in recent decades, the behavior of atmospheric methane is considerably more complex and is much less understood on account of the spatiotemporal variability of its emissions which include biogenic (e.g. wetlands, ruminants, rice agriculture), thermogenic (fossil fuels), and pyrogenic (i.e. biomass burning) sources. After sustained growth during most of the 20th century, the CH4 growth rate declined falling from 15 ppbv/yr during the 1980s to 6 ppbv/yr in the 1990s to near-zero and even negative values in the early 2000s. With some surprise however, the growth rate rebounded in 2007 and has been on average 6 ppbv/yr during the past 10 years. During this same period the 13CH4/12CH4 ratio of atmospheric CH4 also declined suggesting the recent CH4 growth was caused by an increase in 13CH4-depleted biogenic emissions. Here, we provide additional insight into the recent behavior of atmospheric methane by performing a global three-dimensional Bayesian inversion of surface CH4 and 13CH4/12CH4 ratios over the period 1985-2015 using NOAA Global Monitoring Division (GMD) CH4 measurements and the GEOS-Chem chemical-transport model (CTM) at a horizontal grid resolution of 2ox2.5o. The use of the 3-D model allows us to exploit spatial patterns in the global CH4 and 13CH4/12CH4 fields that provide additional constraints on the retrieval of the time-dependent CH4 fluxes. This work follows up on our previous CH4 inversion where we used a 4ox5o horizontal grid for GEOS-Chem to retrieve fluxes from 1985 to 2009. At higher resolution more information is extracted from the observations due to improved model skill and a smaller number of stations aggregated within model grid cells. This increases the

Constraining the sources of CH4 emissions during past abrupt climate change using CH4 triple isotopes mass balance from the ice core records

NASA Astrophysics Data System (ADS)

Dyonisius, M.; Petrenko, V. V.; Smith, A. W.; Hmiel, B.; Beck, J.; Seth, B.; Bock, M.; Hua, Q.; Yang, B.; Harth, C. M.; Beaudette, R.; Lee, J.; Erhardt, T.; Schmitt, J.; Brook, E.; Weiss, R. F.; Fischer, H.; Severinghaus, J. P.

2017-12-01

Methane (CH4) is the third most important greenhouse gas in the atmosphere after water vapor and CO2. Understanding how the natural CH4 budget has changed in response to changing climate in the past can provide insights on the sensitivity of the natural CH4 emissions to the current anthropogenic warming. CH4 isotopes (Δ14CH4, δ13C-CH4, and δD-CH4) from ice cores can be used to fingerprint the sources of CH4 increases in the past. We have successfully extracted 6 large volume (>1000kg) ice core samples from Taylor Glacier, Antarctica spanning the Oldest Dryas-Bølling transition ( 14.7ka) - the first abrupt warming and CH4 rise since the Last Glacial Maximum. Among the CH4 isotopes, our Δ 14CH4 data are unique in their ability to unambiguously distinguish between "old" CH4 sources (e.g. marine clathrate, geologic sources, old permafrost) and "modern" CH4 sources (e.g. tropical and boreal wetlands). Our Δ14CH4 data unambiguously rule out marine clathrate and old permafrost as the sources of the abrupt CH4 rise. Preliminary CH4 stable isotopes box modeling combined with interpolar CH4 concentration gradient from existing ice core records suggest that tropical wetlands were the dominant driver for the Oldest Dryas-Bølling CH4 rise.

Subsoil methanogenesis as source of stem CH4 emission in upland forest trees: preferential CH4 transport via the root system?

NASA Astrophysics Data System (ADS)

Maier, M.; Machacova, K.; Urban, O.; Friederike, L.

2016-12-01

Quantifying and understanding green house gas fluxes in natural soil-plant-atmosphere systems are crucial to predicting global climate change. Wetland species or trees at waterlogged sites are known to emit large amounts of CH4. Yet upland forest soils are regarded as CH4 sinks and tree species like upland European beech (Fagus sylvatica, L.) are assumed not to emit CH4. We studied the soil-atmosphere and stem-atmosphere fluxes of CH4, and soil gas profiles at two upland beech forest sites in Central Europe. Soil was a net CH4 sink at both. Unusually there was one beech tree with substantial CH4 emissions that were higher than the CH4 sink of the soil. The soil gas profile at this tree indicated CH4 production at a soil depth >0.3 m, despite the net uptake of CH4 observed at the soil surface adjacent to the tree. Field soil assessment showed strong redoximorphic color patterns in the adjacent soil. We think that there is a transport link between the soil and stem via the root system representing a preferential transport mechanism for CH4 despite the fact that beech roots usually do not bear aerenchyma. The gas transport process , either via dissolved CH4 in the xylem water or in the root gas phase, is not yet clear. The observed CH4 stem emissions represent an important CH4flux in this ecosystem, und thus should be considered in future research. AcknowledgementThis research was financially supported by the Czech Academy of Sciences and the German Academic Exchange Service within the project "Methane (CH4) and nitrous oxide (N2O) emissions from Fagus sylvatica trees" (DAAD-15-03), National Programme for Sustainability I (LO1415) and project DFG (MA 5826/2-1). We would like to thank Marek Jakubik, Katerina Svobodova, Sinikka Paulus, Ellen Halaburt and Sally Haddad for technical support.

High Resolution CH4 Emissions and Dissolved CH4 Measurements Elucidate Surface Gas Exchange Processes in Toolik Lake, Arctic Alaska

NASA Astrophysics Data System (ADS)

Del Sontro, T.; Sollberger, S.; Kling, G. W.; Shaver, G. R.; Eugster, W.

2013-12-01

Approximately 14% of the Alaskan North Slope is covered in lakes of various sizes and depths. Diffusive carbon emissions (CH4 and CO2) from these lakes offset the tundra sink by ~20 %, but the offset would substantially increase if ebullitive CH4 emissions were also considered. Ultimately, arctic lake CH4 emissions are not insignificant in the global CH4 budget and their contribution is bound to increase due to impacts from climate change. Here we present high resolution CH4 emission data as measured via eddy covariance and a Los Gatos gas analyzer during the ice free period from Toolik Lake, a deep (20 m) Arctic lake located on the Alaskan North Slope, over the last few summers. Emissions are relatively low (< 25 mg CH4 m-2 d-1) with little variation over the summer. Diurnal variations regularly occur, however, with up to 3 times higher fluxes at night. Gas exchange is a relatively difficult process to estimate, but is normally done so as the product of the CH4 gradient across the air-water interface and the gas transfer velocity, k. Typically, k is determined based on the turbulence on the water side of the interface, which is most commonly approximated by wind speed; however, it has become increasingly apparent that this assumption does not remain valid across all water bodies. Dissolved CH4 profiles in Toolik revealed a subsurface peak in CH4 at the thermocline of up to 3 times as much CH4 as in the surface water. We hypothesize that convective mixing at night due to cooling surface waters brings the subsurface CH4 to the surface and causes the higher night fluxes. In addition to high resolution flux emission estimates, we also acquired high resolution data for dissolved CH4 in surface waters of Toolik Lake during the last two summers using a CH4 equilibrator system connected to a Los Gatos gas analyzer. Thus, having both the flux and the CH4 gradient across the air-water interface measured directly, we can calculate k and investigate the processes influencing

Low-concentration kinetics of atmospheric CH{sub 4} oxidation in soil and mechanism of NH{sub 4}{sup +} inhibition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gulledge, J.; Schimel, J.P.

1998-11-01

NH{sub 4}{sup +} inhibition kinetics for CH{sub 4} oxidation were examined at near-atmospheric CH{sub 4} concentrations in three upland forest soils. Whether NH{sub 4}{sup +}-independent salt effects could be neutralized by adding nonammoniacal salts to control samples in lieu of deionized water was also investigated. Because the levels of exchangeable endogenous NH{sub 4}{sup +} were very low in the three soils, desorption of endogenous NH{sub 4}{sup +} was not a significant factor in this study. The K{sub m(app)} values for water-treated controls were 9.8, 22, and 57 nM for temperate pine, temperate hardwood, and birch taiga soils, respectively. At CH{submore » 4} concentrations of {le}15 {micro}l liter{sup {minus}1}, oxidation followed first-order kinetics in the fine-textured taiga soil, whereas the coarse-textured temperate soils exhibited Michaelis-Menten kinetics. Compared to water controls, the K{sub m(app)} values in the temperate soils increased in the presence of NH{sub 4}{sup +} salts, whereas the V{sub max(app)} values decreased substantially, indicating that there was a mixture of competitive and noncompetitive inhibition mechanisms for whole NH{sub 4}{sup +} salts. Compared to the corresponding K{sup +} salt controls, the K{sub m(app)} values for NH{sub 4}{sup +} salts increased substantially, whereas the V{sub max(app)} values remained virtually unchanged, indicating that NH{sub 4}{sup +} acted by competitive inhibition. Nonammoniacal salts caused inhibition to increase with increasing CH{sub 4} concentrations in all three soils. In the birch taiga soil, this trend occurred with both NH{sub 4}{sup +} and K{sup +} salts, and the slope of the increase was not affected by the addition of NH{sub 4}{sup +}. Hence, the increase in inhibition resulted from an NH{sub 4}{sup +}-independent mechanism.« less

Temperature Effects on Microbial CH4 and CO2 Production in Permafrost-Affected Soils From the Barrow Environmental Observatory

NASA Astrophysics Data System (ADS)

Graham, D. E.; Roy Chowdhury, T.; Zheng, J.; Moon, J. W.; Yang, Z.; Gu, B.; Wullschleger, S. D.

2015-12-01

Warmer Arctic temperatures are increasing the annual soil thaw depth and prolonging the thaw season in Alaskan permafrost zones. This change exposes organic matter buried in the soils and permafrost to microbial degradation and mineralization to form CO2 and CH4. The proportion and fluxes of these greenhouse gases released into the atmosphere control the global feedback on warming. To improve representations of these biogeochemical processes in terrestrial ecosystem models we compared soil properties and microbial activities in core samples of polygonal tundra from the Barrow Environmental Observatory. Measurements of soil water potential through the soil column characterized water binding to the organic and mineral components. This suction combines with temperature to control freezing, gas diffusion and microbial activity. The temperature-dependence of CO2 and CH4 production from anoxic soil incubations at -2, +4 or +8 °C identified a significant lag in methanogenesis relative to CO2 production by anaerobic respiration and fermentation. Changes in the abundance of methanogen signature genes during incubations indicate that microbial population shifts caused by thawing and warmer temperatures drive changes in the mixtures of soil carbon degradation products. Comparisons of samples collected across the microtopographic features of ice-wedge polygons address the impacts of water saturation, iron reduction and organic matter content on CH4 production and oxidation. These combined measurements build process understanding that can be applied across scales to constrain key response factors in models that address Arctic soil warming.

Global Inverse Modeling of CH4 and δ13C-CH4 Measurements to Understand Recent Trends in Methane Emissions

NASA Astrophysics Data System (ADS)

Karmakar, S.; Butenhoff, C. L.; Rice, A. L.; Khalil, A. K.

2017-12-01

Methane (CH4) is the second most important greenhouse gas with a radiative forcing of 0.97 W/m2 including both direct and indirect effects and a global warming potential of 28 over a 100-year time horizon. After a decades-long period of decline beginning in the 1980s, the methane growth rate rebounded in 2007 for reasons that are of current debate. During this same growth period atmospheric methane became less enriched in the 13CH4 isotope suggesting the recent CH4 growth was caused by an increase in 13CH4-depleted biogenic emissions. Recent papers have attributed this growth to increasing emissions from wetlands, rice agriculture, and ruminants. In this work we provide additional insight into the recent behavior of atmospheric methane and global wetland emissions by performing a three-dimensional Bayesian inversion of surface CH4 and 13CH4/12CH4 ratios using NOAA Global Monitoring Division (GMD) "event-level" CH4 measurements and the GEOS-Chem chemical-transport model (CTM) at a horizontal grid resolution of 2ox2.5o. The spatial pattern of wetland emissions was prescribed using soil moisture and temperature from GEOS-5 meteorology fields and soil carbon pools from the Lund-Potsdam-Jena global vegetation model. In order to reduce the aggregation error caused by a potentially flawed distribution and to account for isotopic measurements that indicate northern high latitude wetlands are isotopically depleted in 13CH4 relative to tropical wetlands we separated our pattern into three latitudinal bands (90-30°N, 30°N-0, 0-90°S). Our preliminary results support previous claims that the recent increase in atmospheric methane is driven by increases in biogenic CH4 emissions. We find that while wetland emissions from northern high latitudes (90-30°N) remained relatively constant during this time, southern hemisphere wetland emissions rebounded from a decade-long decline and began to rise again in 2007 and have remained elevated to the present. Emissions from rice

Factors Related with CH4 and N2O Emissions from a Paddy Field: Clues for Management implications

PubMed Central

Wang, Chun; Lai, Derrick Y. F.; Sardans, Jordi; Wang, Weiqi; Zeng, Congsheng; Peñuelas, Josep

2017-01-01

Paddy fields are major sources of global atmospheric greenhouse gases, including methane (CH4) and nitrous oxide (N2O). The different phases previous to emission (production, transport, diffusion, dissolution in pore water and ebullition) despite well-established have rarely been measured in field conditions. We examined them and their relationships with temperature, soil traits and plant biomass in a paddy field in Fujian, southeastern China. CH4 emission was positively correlated with CH4 production, plant-mediated transport, ebullition, diffusion, and concentration of dissolved CH4 in porewater and negatively correlated with sulfate concentration, suggesting the potential use of sulfate fertilizers to mitigate CH4 release. Air temperature and humidity, plant stem biomass, and concentrations of soil sulfate, available N, and DOC together accounted for 92% of the variance in CH4 emission, and Eh, pH, and the concentrations of available N and Fe3+, leaf biomass, and air temperature 95% of the N2O emission. Given the positive correlations between CH4 emission and DOC content and plant biomass, reduce the addition of a carbon substrate such as straw and the development of smaller but higher yielding rice genotypes could be viable options for reducing the release of greenhouse gases from paddy fields to the atmosphere. PMID:28081161

Ice core δD(CH4) record precludes marine hydrate CH4 emissions at the onset of Dansgaard-Oeschger events

NASA Astrophysics Data System (ADS)

Bock, M.; Schmitt, J.; Möller, L.; Spahni, R.; Blunier, T.; Fischer, H.

2010-12-01

Air enclosures in polar ice cores represent the only direct paleoatmospheric archive (besides firn air) and show that atmospheric CH4 concentrations changed in concert with northern hemisphere temperature during both glacial/interglacial transitions as well as rapid climate changes (Dansgaard-Oeschger events). For stadials and interstadials during Marine Isotope Stage 3 concentration jumps of 100 - 200 ppbv within a few decades are observed. A concentration gradient with higher values in the northern versus the southern hemisphere during warm stages was reconstructed from ice core methane data from Greenland and Antarctica. This gradient indicates additional methane emissions during warm periods located in the northern hemisphere. However, the underlying processes for these changes are still not well understood. With tropical and boreal wetlands, biomass burning, thermokarst lakes, ruminants, termites, UV-induced emissions from organic matter and marine gas hydrates all contributing to the natural atmospheric CH4 level, an unambiguous source attribution remains difficult. Also changes in the methane sinks can modify the tropospheric CH4 budget, as trace gases like volatile organic compounds are competing for the major reactant - the OH radical. Additionally, the changing global atmospheric methane concentration itself feeds back on its lifetime. Together with the CH4 interhemispheric gradient, stable hydrogen and carbon isotopic studies on methane (δD(CH4) and δ13CH4) in ice cores allow to constrain individual CH4 source/sink changes. Here we present clear evidence from the North Greenland Ice Core Project ice core based on the hydrogen isotopic composition of methane δD(CH4) that clathrates did not cause atmospheric methane concentration to rise at the onset of Dansgaard-Oeschger (DO) events 7 and 8 (34 - 41 kilo years before present), however, we can not exclude that they played a minor role during and at the end of an interstadial. Box modeling supports

Shipboard measurements and modeling of the distribution of CH4 and 13CH4 in the western Pacific

NASA Astrophysics Data System (ADS)

Bromley, T.; Allan, W.; Martin, R.; Mikaloff Fletcher, S. E.; Lowe, D. C.; Struthers, H.; Moss, R.

2012-02-01

We present observations of methane (CH4) mixing ratio and 13C/12C isotopic ratios in CH4 (δ13C) data from a collaborative shipboard project using bulk carrier ships sailing between Nelson, New Zealand, and Osaka, Japan, in the western Pacific Ocean. Measurements of the CH4 mixing ratio and δ13C in CH4were obtained from large clean-air samples collected in each 2.5° to 5° of latitude between 30°S and 30°N on eight voyages from 2004 to 2007. The data show large variations in CH4 mixing ratio in the tropical western Pacific, and data analysis suggests that these large variations are related to the positions and strengths of the South Pacific Convergence Zone and the Intertropical Convergence Zone, with variability in the sources playing a much smaller role. These measurements are compared with results from a modified version of the Unified Model (UMeth) general circulation model along two transects, one similar to the ship transects and another 18.75° to the east. Although UMeth was run to a steady state with the same sources and sinks each year, the gradient structures varied considerably from year to year, supporting our conclusion that variability in transport is a major driver for the observed variations in CH4. Simulations forced with an idealized representation of the El Niño-Southern Oscillation (ENSO) suggest that a large component of the observed variability in latitudinal gradients of CH4 and its δ13C arises from intrinsic variability in the climate system that does not occur on ENSO time scales.

CH4 production via CO2 reduction in a temperate bog - A source of (C-13)-depleted CH4

NASA Technical Reports Server (NTRS)

Lansdown, J. M.; Quay, P. D.; King, S. L.

1992-01-01

The paper reports measurements, taken over two annual cycles, of the flux and delta(C-13) of CH4 released from an acidic peat bog located in the foothills of the Cascade Range in Washington state, U.S. Measurements of the rate of aceticlastic methanogenesis and CO2 reduction in peat soil, using (C-14)-labeled acetate and sodium bicarbonate, show that acetate was not an important CH4 precursor and that CO2 reduction could account for all of the CH4 production. The in situ kinetic isotope effect for CO2 reduction, calculated using the delta-(C-13) of soil water CO2 and CH4 flux, was 0.932 +/- 0.007.

Two-wavelength single laser CH and CH(4) imaging in a lifted turbulent diffusion flame.

PubMed

Namazian, M; Schmitt, R L; Long, M B

1988-09-01

A new technique has been developed which allows simultaneous 2-D mapping of CH and CH 4 in a turbulent methane flame. A flashlamp-pumped dye laser using two back mirrors produces output at 431.5 and 444 nm simultaneously. The 431.5-nm line is used to excite the (0, 0) band of the A(2)Delta-X(2)Pi system of CH, and the fluorescence of the (0, 1) transition is observed at 489 nm. Coincidentally, the spontaneous Raman scattering from CH(4) also occurs near 489 nm for a 431.5-nm excitation. To separate the CH(4) and CH contributions, the 444-nm line is used to produce a spontaneous Raman signal from CH(4) that is spectrally separated from the CH fluorescence. Subtraction of the signals generated by the 431.5- and 444-nm wavelength beams yields separate measurements of CH(4) and CH. Raman-scattered light records the instantaneous distribution of the fuel, and simultaneously the CH fluorescence indicates the location of the flame zone. The resulting composite images provide important insight on the interrelationship between fuel-air mixing and subsequent combustion.M. Namazian is with Altex Technologies Corporation, 109 Via De Tesoros, Los Gatos, California 95030; R. L. Schmitt is with Sandia National Laboratories, Combustion Research Facility, Livermore, California 94550; and M. B. Long is with Yale University, Department of Mechanical Engineering, New Haven, Connecticut 06520.

ANALYSIS OF FACTORS AFFECTING METHANE GAS RECOVERY FROM SIX LANDFILLS

EPA Science Inventory

The report gives results of a pilot study of six U.S. landfills that have methane (CH4) gas recovery systems. NOTE: The study was a first step in developing a field testing program to gather data to identify key variables that affect CH4 generation and to develop an empirical mod...

Thermodynamic and hydrochemical controls on CH4 in a coal seam gas and overlying alluvial aquifer: new insights into CH4 origins

PubMed Central

Owen, D. Des. R.; Shouakar-Stash, O.; Morgenstern, U.; Aravena, R.

2016-01-01

Using a comprehensive data set (dissolved CH4, δ13C-CH4, δ2H-CH4, δ13C-DIC, δ37Cl, δ2H-H2O, δ18O-H2O, Na, K, Ca, Mg, HCO3, Cl, Br, SO4, NO3 and DO), in combination with a novel application of isometric log ratios, this study describes hydrochemical and thermodynamic controls on dissolved CH4 from a coal seam gas reservoir and an alluvial aquifer in the Condamine catchment, eastern Surat/north-western Clarence-Moreton basins, Australia. δ13C-CH4 data in the gas reservoir (−58‰ to −49‰) and shallow coal measures underlying the alluvium (−80‰ to −65‰) are distinct. CO2 reduction is the dominant methanogenic pathway in all aquifers, and it is controlled by SO4 concentrations and competition for reactants such as H2. At isolated, brackish sites in the shallow coal measures and alluvium, highly depleted δ2H-CH4 (<310‰) indicate acetoclastic methanogenesis where SO4 concentrations inhibit CO2 reduction. Evidence of CH4 migration from the deep gas reservoir (200–500 m) to the shallow coal measures (<200 m) or the alluvium was not observed. The study demonstrates the importance of understanding CH4 at different depth profiles within and between aquifers. Further research, including culturing studies of microbial consortia, will improve our understanding of the occurrence of CH4 within and between aquifers in these basins. PMID:27578542

Factors Affecting Teen Involvement in Pennsylvania 4-H Programming

ERIC Educational Resources Information Center

Gill, Bart E.; Ewing, John C.; Bruce, Jacklyn A.

2010-01-01

The study reported here determined the factors that affect teen involvement in 4-H programming. The design of the study was descriptive and correlational in nature. Using a purposive sampling procedure, a survey questionnaire was distributed to all (N=214) 4-H members attending the 4-H State Leadership Conference. The major findings of the study…

Isotopic signatures of anthropogenic CH4 sources in Alberta, Canada

NASA Astrophysics Data System (ADS)

Lopez, M.; Sherwood, O. A.; Dlugokencky, E. J.; Kessler, R.; Giroux, L.; Worthy, D. E. J.

2017-09-01

A mobile system was used for continuous ambient measurements of stable CH4 isotopes (12CH4 and 13CH4) and ethane (C2H6). This system was used during a winter mobile campaign to investigate the CH4 isotopic signatures and the C2H6/CH4 ratios of the main anthropogenic sources of CH4 in the Canadian province of Alberta. Individual signatures were derived from δ13CH4 and C2H6 measurements in plumes arriving from identifiable single sources. Methane emissions from beef cattle feedlots (n = 2) and landfill (n = 1) had δ13CH4 signatures of -66.7 ± 2.4‰ and -55.3 ± 0.2‰, respectively. The CH4 emissions associated with the oil or gas industry had distinct δ13CH4 signatures, depending on the formation process. Emissions from oil storage tanks (n = 5) had δ13CH4 signatures ranging from -54.9 ± 2.9‰ to -60.6 ± 0.6‰ and non-detectable C2H6, characteristic of secondary microbial methanogenesis in oil-bearing reservoirs. In contrast, CH4 emissions associated with natural gas facilities (n = 8) had δ13CH4 signatures ranging from -41.7 ± 0.7‰ to -49.7 ± 0.7‰ and C2H6/CH4 molar ratios of 0.10 for raw natural gas to 0.04 for processed/refined natural gas, consistent with thermogenic origins. These isotopic signatures and C2H6/CH4 ratios have been used for source discrimination in the weekly atmospheric measurements of stable CH4 isotopes over a two-month winter period at the Lac La Biche (LLB) measurement station, located in Alberta, approximately 200 km northeast of Edmonton. The average signature of -59.5 ± 1.4‰ observed at LLB is likely associated with transport of air after passing over oil industry sources located south of the station.

Methanogenic Pathway and Fraction of CH4 Oxidized in Paddy Fields: Seasonal Variation and Effect of Water Management in Winter Fallow Season

PubMed Central

Zhang, Guangbin; Liu, Gang; Zhang, Yi; Ma, Jing; Xu, Hua; Yagi, Kazuyuki

2013-01-01

A 2-year field and incubation experiment was conducted to investigate δ13C during the processes of CH4 emission from the fields subjected to two water managements (flooding and drainage) in the winter fallow season, and further to estimate relative contribution of acetate to total methanogenesis (Fac) and fraction of CH4 oxidized (Fox) based on the isotopic data. Compared with flooding, drainage generally caused CH4, either anaerobically or aerobically produced, depleted in 13C. There was no obvious difference between the two in transport fractionation factor (εtransport) and δ13C-value of emitted CH4. CH4 emission was negatively related to its δ13C-value in seasonal variation (P<0.01). Acetate-dependent methanogenesis in soil was dominant (60–70%) in the late season, while drainage decreased Fac-value by 5–10%. On roots however, CH4 was mostly produced through H2/CO2 reduction (60–100%) over the season. CH4 oxidation mainly occurred in the first half of the season and roughly 10–90% of the CH4 was oxidized in the rhizosphere. Drainage increased Fox-value by 5–15%, which is possibly attributed to a significant decrease in production while no simultaneous decrease in oxidation. Around 30–70% of the CH4 was oxidized at the soil-water interface when CH4 in pore water was released into floodwater, although the amount of CH4 oxidized therein might be negligible relative to that in the rhizosphere. CH4 oxidation was also more important in the first half of the season in lab conditions and about 5–50% of the CH4 was oxidized in soil while almost 100% on roots. Drainage decreased Fox-value on roots by 15% as their CH4 oxidation potential was highly reduced. The findings suggest that water management in the winter fallow season substantially affects Fac in the soil and Fox in the rhizosphere and roots rather than Fac on roots and Fox at the soil-water interface. PMID:24069259

Assessing fugitive emissions of CH4 from high-pressure gas pipelines

NASA Astrophysics Data System (ADS)

Worrall, Fred; Boothroyd, Ian; Davies, Richard

2017-04-01

The impact of unconventional natural gas production using hydraulic fracturing methods from shale gas basins has been assessed using life-cycle emissions inventories, covering areas such as pre-production, production and transmission processes. The transmission of natural gas from well pad to processing plants and its transport to domestic sites is an important source of fugitive CH4, yet emissions factors and fluxes from transmission processes are often based upon ver out of date measurements. It is important to determine accurate measurements of natural gas losses when compressed and transported between production and processing facilities so as to accurately determine life-cycle CH4 emissions. This study considers CH4 emissions from the UK National Transmission System (NTS) of high pressure natural gas pipelines. Mobile surveys of CH4 emissions using a Picarro Surveyor cavity-ring-down spectrometer were conducted across four areas in the UK, with routes bisecting high pressure pipelines and separate control routes away from the pipelines. A manual survey of soil gas measurements was also conducted along one of the high pressure pipelines using a tunable diode laser. When wind adjusted 92 km of high pressure pipeline and 72 km of control route were drive over a 10 day period. When wind and distance adjusted CH4 fluxes were significantly greater on routes with a pipeline than those without. The smallest leak detectable was 3% above ambient (1.03 relative concentration) with any leaks below 3% above ambient assumed ambient. The number of leaks detected along the pipelines correlate to the estimated length of pipe joints, inferring that there are constant fugitive CH4 emissions from these joints. When scaled up to the UK's National Transmission System pipeline length of 7600 km gives a fugitive CH4 flux of 4700 ± 2864 kt CH4/yr - this fugitive emission from high pressure pipelines is 0.016% of the annual gas supply.

Diurnal variability of CO2 and CH4 emissions from tropical reservoirs

NASA Astrophysics Data System (ADS)

Linkhorst, Annika; Reinaldo Paranaíba, José; Barros, Nathan; DelSontro, Tonya; Isidorova, Anastasija; Mendonça, Raquel; Sobek, Sebastian

2017-04-01

Reservoirs are important atmospheric sources of carbon dioxide (CO2) and methane (CH4) with CH4 being a greenhouse gas (GHG) at least 28 times more potent than CO2. Reservoir GHG emissions tend to be heterogeneous, however, and thus current emission estimates are likely conservative since they often overlook emission hot spots and hot moments, especially for CH4 ebullition. For CO2, diffusion is the dominant flux pathway, and diurnal patterns in CO2 emissions can largely be linked to photosynthesis. In contrast, ebullition, the release of gases through bubbles that are formed in the sediments and travel through the water column, is a major emission pathway for CH4 in shallow waters. We visually observed a change in quantity and size of bubbles at different times of the day, and therefore conducted a diurnal study in four different Brazilian reservoirs of different size, age, climatic and geographic characteristics. We hypothesized that sub-daily trends in CH4 ebullition occur in Brazilian reservoirs as bubble release depends on physical factors such as turbulence and hydrostatic pressure, which can exhibit sub-daily patterns in large, managed reservoirs. In each reservoir, we performed measurements of CO2 and CH4 fluxes at one location over 24 hours. CH4 ebullition was tracked continuously by an echosounder, and 13 anchored bubble traps per reservoir were sampled every three hours. Further, a custom-built equilibrator monitored dissolved CH4 and CO2 concentrations, and diffusive and total fluxes of CO2 and CH4 were measured using floating chambers in triplicates every 30 minutes during the same period. We observed that CH4 ebullition as well as CH4 and CO2 diffusion peaked during the day, with peak fluxes being up to four times higher than low fluxes. However, the exact timing and magnitude varied for the different sampling events, and could in part be linked to biological and physical properties of the respective reservoir. This study combined different state

Microbial CH4 and N2O Consumption in Acidic Wetlands

PubMed Central

Kolb, Steffen; Horn, Marcus A.

2012-01-01

Acidic wetlands are global sources of the atmospheric greenhouse gases methane (CH4), and nitrous oxide (N2O). Consumption of both atmospheric gases has been observed in various acidic wetlands, but information on the microbial mechanisms underlying these phenomena is scarce. A substantial amount of CH4 is consumed in sub soil by aerobic methanotrophs at anoxic–oxic interfaces (e.g., tissues of Sphagnum mosses, rhizosphere of vascular plant roots). Methylocystis-related species are likely candidates that are involved in the consumption of atmospheric CH4 in acidic wetlands. Oxygen availability regulates the activity of methanotrophs of acidic wetlands. Other parameters impacting on the methanotroph-mediated CH4 consumption have not been systematically evaluated. N2O is produced and consumed by microbial denitrification, thus rendering acidic wetlands as temporary sources or sinks for N2O. Denitrifier communities in such ecosystems are diverse, and largely uncultured and/or new, and environmental factors that control their consumption activity are unresolved. Analyses of the composition of N2O reductase genes in acidic wetlands suggest that acid-tolerant Proteobacteria have the potential to mediate N2O consumption in such soils. Thus, the fragmented current state of knowledge raises open questions concerning methanotrophs and denitrifiers that consume atmospheric CH4 and N2O in acidic wetlands. PMID:22403579

Mapping pan-Arctic CH4 emissions using an adjoint method by integrating process-based wetland and lake biogeochemical models and atmospheric CH4 concentrations

NASA Astrophysics Data System (ADS)

Tan, Z.; Zhuang, Q.; Henze, D. K.; Frankenberg, C.; Dlugokencky, E. J.; Sweeney, C.; Turner, A. J.

2015-12-01

Understanding CH4 emissions from wetlands and lakes are critical for the estimation of Arctic carbon balance under fast warming climatic conditions. To date, our knowledge about these two CH4 sources is almost solely built on the upscaling of discontinuous measurements in limited areas to the whole region. Many studies indicated that, the controls of CH4 emissions from wetlands and lakes including soil moisture, lake morphology and substrate content and quality are notoriously heterogeneous, thus the accuracy of those simple estimates could be questionable. Here we apply a high spatial resolution atmospheric inverse model (nested-grid GEOS-Chem Adjoint) over the Arctic by integrating SCIAMACHY and NOAA/ESRL CH4 measurements to constrain the CH4 emissions estimated with process-based wetland and lake biogeochemical models. Our modeling experiments using different wetland CH4 emission schemes and satellite and surface measurements show that the total amount of CH4 emitted from the Arctic wetlands is well constrained, but the spatial distribution of CH4 emissions is sensitive to priors. For CH4 emissions from lakes, our high-resolution inversion shows that the models overestimate CH4 emissions in Alaskan costal lowlands and East Siberian lowlands. Our study also indicates that the precision and coverage of measurements need to be improved to achieve more accurate high-resolution estimates.

Raman spectroscopy measurement of CH4 gas and CH4 dissolved in water for laser remote sensing in water

NASA Astrophysics Data System (ADS)

Somekawa, Toshihiro; Fujita, Masayuki

2018-04-01

We examined the applicability of Raman spectroscopy as a laser remote sensing tool for monitoring CH4 in water. The Raman technique has already been used successfully for measurements of CO2 gas in water. In this paper, considering the spectral transmittance of water, third harmonics of Q-switched Nd:YAG laser at 355 nm (UV region) was used for detection of CH4 Raman signals. The Raman signal at 2892 cm-1 from CH4 dissolved in water was detected at a tail of water Raman signal.

Uncertainties in modelling CH4 emissions from northern wetlands in glacial climates: the role of vegetation parameters

NASA Astrophysics Data System (ADS)

Berrittella, C.; van Huissteden, J.

2011-10-01

Marine Isotope Stage 3 (MIS 3) interstadials are marked by a sharp increase in the atmospheric methane (CH4) concentration, as recorded in ice cores. Wetlands are assumed to be the major source of this CH4, although several other hypotheses have been advanced. Modelling of CH4 emissions is crucial to quantify CH4 sources for past climates. Vegetation effects are generally highly generalized in modelling past and present-day CH4 fluxes, but should not be neglected. Plants strongly affect the soil-atmosphere exchange of CH4 and the net primary production of the vegetation supplies organic matter as substrate for methanogens. For modelling past CH4 fluxes from northern wetlands, assumptions on vegetation are highly relevant since paleobotanical data indicate large differences in Last Glacial (LG) wetland vegetation composition as compared to modern wetland vegetation. Besides more cold-adapted vegetation, Sphagnum mosses appear to be much less dominant during large parts of the LG than at present, which particularly affects CH4 oxidation and transport. To evaluate the effect of vegetation parameters, we used the PEATLAND-VU wetland CO2/CH4 model to simulate emissions from wetlands in continental Europe during LG and modern climates. We tested the effect of parameters influencing oxidation during plant transport (fox), vegetation net primary production (NPP, parameter symbol Pmax), plant transport rate (Vtransp), maximum rooting depth (Zroot) and root exudation rate (fex). Our model results show that modelled CH4 fluxes are sensitive to fox and Zroot in particular. The effects of Pmax, Vtransp and fex are of lesser relevance. Interactions with water table modelling are significant for Vtransp. We conducted experiments with different wetland vegetation types for Marine Isotope Stage 3 (MIS 3) stadial and interstadial climates and the present-day climate, by coupling PEATLAND-VU to high resolution climate model simulations for Europe. Experiments assuming dominance of

Rate Coefficient for the (4)Heμ + CH4 Reaction at 500 K: Comparison between Theory and Experiment.

PubMed

Arseneau, Donald J; Fleming, Donald G; Li, Yongle; Li, Jun; Suleimanov, Yury V; Guo, Hua

2016-03-03

The rate constant for the H atom abstraction reaction from methane by the muonic helium atom, Heμ + CH4 → HeμH + CH3, is reported at 500 K and compared with theory, providing an important test of both the potential energy surface (PES) and reaction rate theory for the prototypical polyatomic CH5 reaction system. The theory used to characterize this reaction includes both variational transition-state (CVT/μOMT) theory (VTST) and ring polymer molecular dynamics (RPMD) calculations on a recently developed PES, which are compared as well with earlier calculations on different PESs for the H, D, and Mu + CH4 reactions, the latter, in particular, providing for a variation in atomic mass by a factor of 36. Though rigorous quantum calculations have been carried out for the H + CH4 reaction, these have not yet been extended to the isotopologues of this reaction (in contrast to H3), so it is important to provide tests of less rigorous theories in comparison with kinetic isotope effects measured by experiment. In this regard, the agreement between the VTST and RPMD calculations and experiment for the rate constant of the Heμ + CH4 reaction at 500 K is excellent, within 10% in both cases, which overlaps with experimental error.

Chemical and isotopic equilibrium between CO 2 and CH 4 in fumarolic gas discharges: Generation of CH 4 in arc magmatic-hydrothermal systems

NASA Astrophysics Data System (ADS)

Fiebig, Jens; Chiodini, Giovanni; Caliro, Stefano; Rizzo, Andrea; Spangenberg, Jorge; Hunziker, Johannes C.

2004-05-01

The chemical and isotopic composition of fumarolic gases emitted from Nisyros Volcano, Greece, and of a single gas sample from Vesuvio, Italy, was investigated in order to determine the origin of methane (CH 4) within two subduction-related magmatic-hydrothermal environments. Apparent temperatures derived from carbon isotope partitioning between CH 4 and CO 2 of around 340°C for Nisyros and 470°C for Vesuvio correlate well with aquifer temperatures as measured directly and/or inferred from compositional data using the H 2O-H 2-CO 2-CO-CH 4 geothermometer. Thermodynamic modeling reveals chemical equilibrium between CH 4, CO 2 and H 2O implying that carbon isotope partitioning between CO 2 and CH 4 in both systems is controlled by aquifer temperature. N 2/ 3He and CH 4/ 3He ratios of Nisyros fumarolic gases are unusually low for subduction zone gases and correspond to those of midoceanic ridge environments. Accordingly, CH 4 may have been primarily generated through the reduction of CO 2 by H 2 in the absence of any organic matter following a Fischer-Tropsch-type reaction. However, primary occurrence of minor amounts of thermogenic CH 4 and subsequent re-equilibration with co-existing CO 2 cannot be ruled out entirely. CO 2/ 3He ratios and δ 13C CO 2 values imply that the evolved CO 2 either derives from a metasomatized mantle or is a mixture between two components, one outgassing from an unaltered mantle and the other released by thermal breakdown of marine carbonates. The latter may contain traces of organic matter possibly decomposing to CH 4 during thermometamorphism.

Tree CH4 fluxes in forestry drained peatland in southern Finland

NASA Astrophysics Data System (ADS)

Haikarainen, Iikka; Putkinen, Anuliina; Pyykkö, Petteri; Halmeenmäki, Elisa; Pihlatie, Mari

2017-04-01

Methane (CH4) is among the most important greenhouse gases and its atmospheric concentration is increasing. Boreal forests are commonly considered a net sink of atmospheric CH4 due to CH4 consuming bacteria in aerated soil layers. Recent studies have, however, demonstrated that trees are capable of emitting CH4 from their stems and shoots by transporting anaerobically produced CH4 from deeper soil layers to the atmosphere. Furthermore, trees may act as independent sources of CH4. We have measured tree stem CH4 exchange of boreal tree species at Lettosuo, a nutrient rich peatland forest in Tammela, southern Finland (60˚ 38' N, 23˚ 57' E), using the static chamber technique. Three species, downy birch (Betula pubescens), Norway spruce (Picea abies) and Scots pine (Pinus sylvestris), were selected under investigation as they represent common boreal tree species. Fluxes of CH4 were measured during 7.6.2016 - 17.10.2016 from in total 25 sample trees growing on two different plots: a treatment plot where all the pines were removed to raise the water table level (WTL) and a control plot. Three birches from the treatment plot were selected to measure CH4 flux variation within vertical profile of the trees. Characterization of microbial communities, quantification of methanogenic and methanotrophic functional genes, and measurements of potential CH4 production and consumption from peat profile and forest floor moss samples were also carried out to obtain insight to the CH4 flux dynamics at the studied sites. The pine removal treatment did not markedly change the average WTL, but it made the WTL more variable with frequently 10-15 cm closer to soil surface compared to the WTL on the control plot. We found small and variable CH4 emissions from the stems of trees on both of the plots, while occasional consumption of CH4 was also present. Generally the CH4 emissions were higher and more dominant at the treatment plot compared to the control plot, and the fluxes were

Enhanced simulations of CH4 and CO2 production in permafrost-affected soils address soil moisture controls on anaerobic decomposition

NASA Astrophysics Data System (ADS)

Graham, D. E.; Zheng, J.; Moon, J. W.; Painter, S. L.; Thornton, P. E.; Gu, B.; Wullschleger, S. D.

2017-12-01

Rapid warming of Arctic ecosystems exposes soil organic carbon (SOC) to accelerated microbial decomposition, leading to increased emissions of carbon dioxide (CO2) and methane (CH4) that have a positive feedback on global warming. The magnitude, timing, and form of carbon release will depend not only on changes in temperature, but also on biogeochemical and hydrological properties of soils. In this synthesis study, we assessed the decomposability of thawed organic carbon from active layer soils and permafrost from the Barrow Environmental Observatory across different microtopographic positions under anoxic conditions. The main objectives of this study were to (i) examine environmental conditions and soil properties that control anaerobic carbon decomposition and carbon release (as both CO2 and CH4); (ii) develop a common set of parameters to simulate anaerobic CO2 and CH4 production; and (iii) evaluate uncertainties generated from representations of pH and temperature effects in the current model framework. A newly developed anaerobic carbon decomposition framework simulated incubation experiment results across a range of soil water contents. Anaerobic CO2 and CH4 production have different temperature and pH sensitivities, which are not well represented in current biogeochemical models. Distinct dynamics of CH4 production at -2° C suggest methanogen biomass and growth rate limit activity in these near-frozen soils, compared to warmer temperatures. Anaerobic CO2 production is well constrained by the model using data-informed labile carbon pool and fermentation rate initialization to accurately simulate its temperature sensitivity. On the other hand, CH4 production is controlled by water content, methanogenesis biomass, and the presence of alternative electron acceptors, producing a high temperature sensitivity with large uncertainties for methanogenesis. This set of environmental constraints to methanogenesis is likely to undergo drastic changes due to permafrost

Decadal changes in CH4 and CO2 emissions on the Alaskan North Slope

NASA Astrophysics Data System (ADS)

Sweeney, C.; Commane, R.; Wofsy, S.; Dlugokencky, E. J.; Karion, A.; Stone, R. S.; Chang, R.; Tans, P. P.; Wolter, S.

2016-12-01

Large changes in surface air temperature, sea ice cover and permafrost in the Arctic Boreal Ecosystems (ABE) are significantly impacting the critical ecosystem services and human societies that are dependent on the ABE. In order to predict the outcome of continued change in the climate system of the ABE, it is necessary to look at how past changes in climate have affected the ABE. We look at 30 years of CH4 and 42 years of CO2 observations from the NOAA Global Greenhouse Gas Reference Network site in Barrow, Alaska. By eliminating background trends and only looking at data collected when winds are blowing off the North Slope we find very little change in CH4 enhancements, but significant changes in the CO2 enhancements coming off the tundra. The bulk of both CO2 and CH4 emissions appear to be emitted well after the first snow fall on the North Slope. CO2 emissions are a strongly correlation with summer surface temperatures, while CH4 emissions appear insensitive to the large temperature changes that occurred over the measurement period. These results suggest that CO2, and not CH4 emissions, are a likely pathway for the degradation of permafrost carbon.

Sensitivity of subtropical wetland CH4 flux predictions to inundation parameterizations: A case study over the southeastern U.S.

NASA Astrophysics Data System (ADS)

Resovsky, A.; Yang, Z. L.

2015-12-01

Methane (CH4) is an important greenhouse gas, and the predominant source of natural atmospheric CH4 globally is its production in wetland soils. Wetlands and marshes in the southeastern U.S. comprise over 40 million acres of land and thus represent a significant component of the global climate system. CH4 contributions from these and other subtropical systems remain difficult to quantify, however. Existing field measurements are lacking in both spatial and temporal coverage, inhibiting efforts to produce regional estimates through upscaling. Top-down constraints on emissions have been generated using satellite remote sensing retrievals of column CH4 (e.g., Frankenberg et al., 2005, 2008, Bergamaschi et al., 2007, 2013, Bloom et al., 2010, Wecht et al., 2014), but such approaches typically require preexisting emissions estimates to discern individual source contributions. Land Surface Models (LSMs) have the potential to produce realistic results, but such predictions rely on accurate representations of sub-grid scale processes responsible for emissions. Since net fluxes are governed by complex interactions between local environmental and biogeochemical factors including water table position, soil temperature, soil substrate availability and vegetation type, reliable flux simulations depend not only upon how such processes are resolved but how skillfully the land surface state itself is predicted by a given model. Here, we examine simulations using CLM4Me, a CH4 biogeochemistry model run within CESM, and compare results to recently compiled flux estimations from satellite remote sensing data. We then examine how seasonal CH4 flux simulations in CLM4Me are affected by alternative parameterizations of inundated land fraction. A global inundation dataset is calculated using DYPTOP, a newly-developed TOPMODEL implementation specifically designed to simulate the dynamics of wetland spatial distribution. We find evidence that DYPTOP may improve wetland CH4 flux predictions

A vacuum ultraviolet laser pulsed field ionization-photoion study of methane (CH 4): Determination of the appearance energy of methylium from methane with unprecedented precision and the resulting impact on the bond dissociation energies of CH 4 and CH 4 +

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chang, Yih -Chung; Xiong, Bo; Bross, David H.

Here, we report on the successful implementation of a high-resolution vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) detection method for the study of unimolecular dissociation of quantum-state- or energy-selected molecular ions. As a test case, we have determined the 0 K appearance energy (AE 0) for the formation of methylium, CH 3 +, from methane, CH 4, as AE 0 (CH 3 +/CH 4) = 14.32271 ± 0.00013 eV. This value has a significantly smaller error limit, but is otherwise consistent with previous laboratory and/or synchrotron-based studies of this dissociative photoionization onset. Furthermore, the sum of the VUV lasermore » PFI-PI spectra obtained for the parent CH 4 + ion and the fragment CH 3 + ions of methane is found to agree with the earlier VUV pulsed field ionization-photoelectron (VUV-PFI-PE) spectrum of methane, providing unambiguous validation of the previous interpretation that the sharp VUV-PFI-PE step observed at the AE 0 (CH 3 +/CH 4) threshold ensues because of higher PFI detection efficiency for fragment CH 3 + than for parent CH 4 +. This, in turn, is a consequence of the underlying high- n Rydberg dissociation mechanism for the dissociative photoionization of CH 4, which was proposed in previous synchrotron-based VUV-PFI-PE and VUV-PFI-PEPICO studies of CH 4. The present highly accurate 0 K dissociative ionization threshold for CH 4 can be utilized to derive accurate values for the bond dissociation energies of methane and methane cation. For methane, the straightforward application of sequential thermochemistry via the positive ion cycle leads to some ambiguity because of two competing VUV-PFI-PE literature values for the ionization energy of methyl radical. The ambiguity is successfully resolved by applying the Active Thermochemical Tables (ATcT) approach, resulting in D 0 (H-CH 3) = 432.463 ± 0.027 kJ/mol and D 0(H-CH 3 +) = 164.701 ± 0.038 kJ/mol.« less

A vacuum ultraviolet laser pulsed field ionization-photoion study of methane (CH 4): Determination of the appearance energy of methylium from methane with unprecedented precision and the resulting impact on the bond dissociation energies of CH 4 and CH 4 +

DOE PAGES

Chang, Yih -Chung; Xiong, Bo; Bross, David H.; ...

2017-03-27

Here, we report on the successful implementation of a high-resolution vacuum ultraviolet (VUV) laser pulsed field ionization-photoion (PFI-PI) detection method for the study of unimolecular dissociation of quantum-state- or energy-selected molecular ions. As a test case, we have determined the 0 K appearance energy (AE 0) for the formation of methylium, CH 3 +, from methane, CH 4, as AE 0 (CH 3 +/CH 4) = 14.32271 ± 0.00013 eV. This value has a significantly smaller error limit, but is otherwise consistent with previous laboratory and/or synchrotron-based studies of this dissociative photoionization onset. Furthermore, the sum of the VUV lasermore » PFI-PI spectra obtained for the parent CH 4 + ion and the fragment CH 3 + ions of methane is found to agree with the earlier VUV pulsed field ionization-photoelectron (VUV-PFI-PE) spectrum of methane, providing unambiguous validation of the previous interpretation that the sharp VUV-PFI-PE step observed at the AE 0 (CH 3 +/CH 4) threshold ensues because of higher PFI detection efficiency for fragment CH 3 + than for parent CH 4 +. This, in turn, is a consequence of the underlying high- n Rydberg dissociation mechanism for the dissociative photoionization of CH 4, which was proposed in previous synchrotron-based VUV-PFI-PE and VUV-PFI-PEPICO studies of CH 4. The present highly accurate 0 K dissociative ionization threshold for CH 4 can be utilized to derive accurate values for the bond dissociation energies of methane and methane cation. For methane, the straightforward application of sequential thermochemistry via the positive ion cycle leads to some ambiguity because of two competing VUV-PFI-PE literature values for the ionization energy of methyl radical. The ambiguity is successfully resolved by applying the Active Thermochemical Tables (ATcT) approach, resulting in D 0 (H-CH 3) = 432.463 ± 0.027 kJ/mol and D 0(H-CH 3 +) = 164.701 ± 0.038 kJ/mol.« less

Valorization of CH4 emissions into high-added-value products: Assessing the production of ectoine coupled with CH4 abatement.

PubMed

Cantera, Sara; Lebrero, Raquel; Sadornil, Lidia; García-Encina, Pedro A; Muñoz, Raúl

2016-11-01

This study assessed an innovative strategy for the valorization of dilute methane emissions based on the bio-conversion of CH4 (the second most important greenhouse gas (GHG)) into ectoine by the methanotrophic ectoine-producing strain Methylomicrobium alcaliphilum 20 Z. The influence of CH4 (2-20%), Cu(2+) (0.05-50 μM) and NaCl (0-9%) concentration as well as temperature (25-35 °C) on ectoine synthesis and specific CH4 biodegradation rate was evaluated for the first time. Concentrations of 20% CH4 (at 3% NaCl, 0.05 μM Cu(2+), 25 °C) and 6% NaCl (at 4% CH4, 0.05 μM Cu(2+), 25 °C) supported the maximum intra-cellular ectoine production yield (31.0 ±1.7 and 66.9 ±4.2 mg g biomass(-1), respectively). On the other hand, extra-cellular ectoine concentrations of up to 4.7 ± 0.1 mg L(-1) were detected at high Cu(2+)concentrations (50 μM), despite this methanotroph has not been previously classified as an ectoine-excreting strain. This research demonstrated the feasibility of the bio-conversion of dilute emissions of methane into high-added value products in an attempt to develop a sustainable GHG bioeconomy. Copyright © 2016 Elsevier Ltd. All rights reserved.

Parallel factor ChIP provides essential internal control for quantitative differential ChIP-seq.

PubMed

Guertin, Michael J; Cullen, Amy E; Markowetz, Florian; Holding, Andrew N

2018-04-17

A key challenge in quantitative ChIP combined with high-throughput sequencing (ChIP-seq) is the normalization of data in the presence of genome-wide changes in occupancy. Analysis-based normalization methods were developed for transcriptomic data and these are dependent on the underlying assumption that total transcription does not change between conditions. For genome-wide changes in transcription factor (TF) binding, these assumptions do not hold true. The challenges in normalization are confounded by experimental variability during sample preparation, processing and recovery. We present a novel normalization strategy utilizing an internal standard of unchanged peaks for reference. Our method can be readily applied to monitor genome-wide changes by ChIP-seq that are otherwise lost or misrepresented through analytical normalization. We compare our approach to normalization by total read depth and two alternative methods that utilize external experimental controls to study TF binding. We successfully resolve the key challenges in quantitative ChIP-seq analysis and demonstrate its application by monitoring the loss of Estrogen Receptor-alpha (ER) binding upon fulvestrant treatment, ER binding in response to estrodiol, ER mediated change in H4K12 acetylation and profiling ER binding in patient-derived xenographs. This is supported by an adaptable pipeline to normalize and quantify differential TF binding genome-wide and generate metrics for differential binding at individual sites.

The Structure of Titan’s N2 and CH4 Coronae

NASA Astrophysics Data System (ADS)

Jiang, Fayu; Cui, Jun; Xu, Jiyao

2017-12-01

In this study, we analyze the structures of Titan’s N2 and CH4 coronae using a large data set acquired by the Ion Neutral Mass Spectrometer (INMS) instrument on board Cassini. The N2 and CH4 densities measured from the exobase up to 2000 km imply a mean exobase temperature of 146 K and 143 K, respectively, which is lower than the mean upper atmospheric temperature by 4 and 7 K. This indicates that on average, Titan possesses a subthermal rather than suprathermal corona. A careful examination reveals that the variability in corona structure is not very likely to be solar driven. Within the framework of the collisionless kinetic model, we investigate how the CH4 energy distribution near the exobase could be constrained if strong CH4 escape occurs on Titan. Several functional forms for the CH4 energy distribution are attempted, assuming two representative CH4 escape rates of 1.2× {10}25 s-1 and 2.2× {10}27 s-1. We find that the double Maxwellian and power-law distributions can reproduce the shape of the CH4 corona structure as well as the imposed CH4 escape rate. In both cases, the escape rate is contributed by a suprathermal CH4 population on the high-energy tail, with a number fraction below 5% and a characteristic energy of 0.1-0.6 eV per suprathermal CH4 molecule. The coexistence of the subthermal CH4 corona revealed by the INMS data and substantial CH4 escape suggested by some previous works could be reconciled by a significant departure in the exobase CH4 energy distribution from ideal Maxwellian that enhances escape and causes a noticeable redistribution of the corona structure.

Infrared observations and laboratory simulations of interstellar CH_4_ and SO_2_.

NASA Astrophysics Data System (ADS)

Boogert, A. C. A.; Schutte, W. A.; Helmich, F. P.; Tielens, A. G. G. M.; Wooden, D. H.

1997-02-01

Interstellar CH_4_ may consume a fair amount of the carbon budget in dense molecular clouds, but probably less than CO, CH_3_OH, and CO_2_. However, it can only be observed at wavelength regions in the infrared that are heavily affected by the earth atmosphere. With new space and airborne missions (e.g. ISO, SOFIA) in mind we have studied the near infrared absorption spectra of solid and gaseous CH_4_. We obtained laboratory spectra of the ν_4_ deformation mode (1302cm^-1^, 7.68μm) of solid CH_4_ in astrophysically relevant mixtures. We found that the peak position and width of this absorption band vary strongly as a function of molecular environment, compared to temperature and particle shape effects. Hence, observations of this feature will provide a powerful probe of the molecular composition of interstellar ices. Also the gas phase CH_4_ ro-vibrational spectrum of the same band has been calculated. Using observed physical conditions around the protostar W 33A, we show that unresolved gaseous CH_4_ lines are detectable (at the 2-5% level) at a resolution R>1000, when the column density N>=10^16^ cm^-2^. An astrophysically relevant molecule with a very strong transition in the same wavelength regime, is SO_2_. We studied the ν _3_ asymmetric stretching mode (1319 cm^-1^, 7.58 μm) of solid SO_2_ in several mixtures, revealing that the peak position, width and detailed profile of this band are very sensitive to the molecular environment. Besides probing the composition of ice mantles, observations of solid SO_2_ will provide important information on the sulfur budget locked up in grain mantles, which is currently poorly known. We compare the laboratory and calculated spectra of CH_4_ and SO_2_ with previously published ground based spectra and new airborne observations of young stellar objects in the 7-8μm region. W 33A, NGC 7538 : IRS1 and IRS9 show a feature near 7.68μm that is consistent with absorption by solid CH_4_ or the Q-branch of gaseous CH_4_. The

Warming Early Mars With CH4

NASA Astrophysics Data System (ADS)

Justh, H. L.; Kasting, J. F.

2002-12-01

The nature of the ancient climate of Mars remains one of the fundamental unresolved problems in martian research. While the present environment is hostile to life, images from the Mariner, Viking and Mars Global Surveyor missions, have shown geologic features on the martian surface that seem to indicate an earlier period of hydrologic activity. The fact that ancient valley networks and degraded craters have been seen on the martian surface indicates that the early martian climate may have been more Earth-like, with a warmer surface temperature. The presence of liquid water would require a greenhouse effect much larger than needed at present, as the solar constant, S0, was 25% lower 3.8 billion years ago when the channels are thought to have formed (1,2). Previous calculations have shown that gaseous CO2 and H2O alone could not have warmed the martian surface to the temperature needed to account for the presence of liquid water (3). It has been hypothesized that a CO2-H2O atmosphere could keep early Mars warm if it was filled with CO2 ice clouds in the upper martian troposphere (4). Obtaining mean martian surface temperatures above 273 K would require nearly 100% cloud cover, a condition that is unrealistic for condensation clouds on early Mars. Any reduction in cloud cover makes it difficult to achieve warm martian surface temperatures except at high pressures and CO2 clouds could cool the martian surface if they were low and optically thick (5). CO2 and CH4 have been suggested as important greenhouse gases on the early Earth. Our research focuses on the effects of increased concentrations of atmospheric greenhouse gases on the surface temperature of early Mars, with emphasis on the reduced greenhouse gas, CH4. To investigate the possible warming effect of CH4, we modified a one-dimensional, radiative-convective climate model used in previous studies of the early martian climate (5). New cloud-free temperature profiles for various surface pressures and CH4 mixing

Flux to the atmosphere of CH4 and CO2 from wetland ponds on the Hudson Bay lowlands (HBLs)

NASA Technical Reports Server (NTRS)

Hamilton, J. David; Kelly, Carol A.; Rudd, John W. M.; Hesslein, Raymond H.; Roulet, Nigel T.

1994-01-01

Ponds on peatlands of the Hudson Bay lowlands (HBLs) are complex ecosystems in which the fluxes to the atmosphere of CH4 and CO2 were controlled by interacting physical and biological factors. This resulted in strong diel variations of both dissolved gas concentrations and gas fluxes to the atmosphere, necessitating frequent sampling on a 24-hour schedule to enable accurate estimates of daily fluxes. Ponds at three sites on the HBL were constant net sources of CH4 and CO2 to the atmosphere at mean rates of 110-180 mg CH4 m(exp -2)/d and 3700-11,000 mg CO2 m(exp -2)/d. Rates peaked in August and September. For CH4 the pond fluxes were 3-30 times higher than adjacent vegetated surfaces. For CO2 the net pond fluxes were similar in magnitude to the vegetated fluxes but the direction of the flux was opposite, toward atmosphere. Even though ponds cover only 8-12% of the HBL area, they accounted for 30% of its total CH4 flux to the atmosphere. There is some circumstantial evidence that the ponds are being formed by decomposition of the underlying peat and that this decomposition is being stimulated by the activity of N2 fixing cyanobacteria that grow in mats at the peat-water interface. The fact that the gas fluxes from the ponds were so different from the surrounding vegetated surfaces means that any change in the ratio of pond to vegetated area, as may occur in response to climate change, would affect the total HBL fluxes.

Enhanced Oxidation Capacity from Photolytic HOx/NOx Recycling: Implications for CH4 Growth

NASA Astrophysics Data System (ADS)

Madronich, S.

2017-12-01

Oxidation by OH radicals converts many emitted compounds (CO, CH4, VOCs as well as NOx, SO2, HCFCs, and others) to more soluble forms that can be removed rapidly from the atmosphere, e.g., by deposition. In a chemically stable atmosphere (without runaway concentration growth) the rate of OH production must generally exceed the emission rates of the reduced compounds, but secondary chemistry complicates OH budgets. If emission rates (e.g., E for CH4) increase, OH concentrations can either decrease or increase depending on NOx conditions, causing a non-linear dependence of CH4 concentrations on its emissions, [CH4] Ef where f, the methane feedback factor, is currently estimated in global 3d models to be 1.3-1.4. This feature is robust among models, and can be reproduced in simpler box models with the canonical Ox-HOx-NOx chemistry, in which global OH is increased by NOx emissions and decreased by CO, CH4, and VOC emissions. Scenarios with lower NOx emissions but higher CH4 emissions point to substantially lower global oxidation capacity in the future. Several newly hypothesized processes have attracted attention in recent years, including the photolytic recycling of OH from biogenic VOCs, and the photolysis of particulate nitrates to regenerate NOx. The latter process could be particularly significant in regions far from NOx emissions, where low NOx levels are more efficient at generating O3 and OH. To the extent that these processes do occur, they may provide some buffering of global OH against CH4 variations (f nearer 1), and more generally against anthropogenic perturbations. However, critical measurements from both lab and field are needed to assess the importance of these proposed processes.

Photosynthates as dominant source of CH4 and CO2 in soil water and CH4 emitted to the atmosphere from paddy fields

NASA Astrophysics Data System (ADS)

Minoda, Tomomi; Kimura, Mamoto; Wada, Eitaro

1996-09-01

Emission rates of CH4 from paddy soil with and without rice straw applications were measured with pot experiments to estimate the contribution of rice straw to the total CH4 emission during the growth period of rice plants. The CH4 derived from rice straw was calculated to be 44% of the total emission. 13CO2 uptake experiments were also carried out four times from June 30 to September 13, 1994, to estimate the contribution of photosynthesized carbon to CH4 emission. The contribution percentages of photosynthesized carbon to the total CH4 emitted to the atmosphere were 3.8% around June 30, 31% around July 25, 30% around August 19, and 14% around September 13 in the treatment with rice straw applications, and 52% around July 25, 28% around August 19, and 15% around September 13 in the treatment without rice straw applications. They were calculated to be 22% and 29% for the entire growth period in the treatments with and without rice straw applications, respectively. The contribution percentages of photosynthesized carbon to the total CH4 and inorganic carbon (Σ CO2) dissolved in soil water were 1.3%, 30%, 29%, and 34% for dissolved CH4 and 3.0%, 36%, 30% and 28% for dissolved inorganic carbon around June 30, July 25, August l9, and September 13, respectively, in the treatment with rice straw applications. They were 70%, 23%, and 32% for dissolved CH4 and 31%, 16%, and 19% for dissolved inorganic carbon around July 25, August 19, and September 13, respectively, in the treatment without rice straw applications.

Contribution of Anthropogenic and Natural Emissions to Global CH4 Balances by Utilizing δ13C-CH4 Observations in CarbonTracker Data Assimilation System (CTDAS)

NASA Astrophysics Data System (ADS)

Kangasaho, V. E.; Tsuruta, A.; Aalto, T.; Backman, L. B.; Houweling, S.; Krol, M. C.; Peters, W.; van der Laan-Luijkx, I. T.; Lienert, S.; Joos, F.; Dlugokencky, E. J.; Michael, S.; White, J. W. C.

2017-12-01

The atmospheric burden of CH4 has more than doubled since preindustrial time. Evaluating the contribution from anthropogenic and natural emissions to the global methane budget is of great importance to better understand the significance of different sources at the global scale, and their contribution to changes in growth rate of atmospheric CH4 before and after 2006. In addition, observations of δ13C-CH4 suggest an increase in natural sources after 2006, which matches the observed increase and variation of CH4 abudance. Methane emission sources can be identified using δ13C-CH4, because different sources produce methane with process-specific isotopic signatures. This study focuses on inversion model based estimates of global anthropogenic and natural methane emission rates to evaluate the existing methane emission estimates with a new δ13C-CH4 inversion system. In situ measurements of atmospheric methane and δ13C-CH4 isotopic signature, provided by the NOAA Global Monitoring Division and the Institute of Arctic and Alpine Research, will be assimilated into the CTDAS-13C-CH4. The system uses the TM5 atmospheric transport model as an observation operator, constrained by ECMWF ERA Interim meteorological fields, and off-line TM5 chemistry fields to account for the atmospheric methane sink. LPX-Bern DYPTOP ecosystem model is used for prior natural methane emissions from wetlands, peatlands and mineral soils, GFED v4 for prior fire emissions and EDGAR v4.2 FT2010 inventory for prior anthropogenic emissions. The EDGAR antropogenic emissions are re-divided into enteric fermentation and manure management, landfills and waste water, rice, coal, oil and gas, and residential emissions, and the trend of total emissions is scaled to match optimized anthropogenic emissions from CTE-CH4. In addition to these categories, emissions from termites and oceans are included. Process specific δ13C-CH4 isotopic signatures are assigned to each emission source to estimate 13CH4 fraction

A pan-Arctic synthesis of CH4 and CO2 production from anoxic soil incubations

USGS Publications Warehouse

Treat, C.C.; Natali, Susan M.; Ernakovich, Jessica; Iverson, Colleen M.; Lupasco, Massimo; McGuire, A. David; Norby, Richard J.; Roy Chowdhury, Taniya; Richter, Andreas; Šantrůčková, Hana; Schädel, C.; Schuur, Edward A.G.; Sloan, Victoria L.; Turetsky, Merritt R.; Waldrop, Mark P.

2015-01-01

Permafrost thaw can alter the soil environment through changes in soil moisture, frequently resulting in soil saturation, a shift to anaerobic decomposition, and changes in the plant community. These changes, along with thawing of previously frozen organic material, can alter the form and magnitude of greenhouse gas production from permafrost ecosystems. We synthesized existing methane (CH4) and carbon dioxide (CO2) production measurements from anaerobic incubations of boreal and tundra soils from the geographic permafrost region to evaluate large-scale controls of anaerobic CO2 and CH4 production and compare the relative importance of landscape-level factors (e.g., vegetation type and landscape position), soil properties (e.g., pH, depth, and soil type), and soil environmental conditions (e.g., temperature and relative water table position). We found fivefold higher maximum CH4 production per gram soil carbon from organic soils than mineral soils. Maximum CH4 production from soils in the active layer (ground that thaws and refreezes annually) was nearly four times that of permafrost per gram soil carbon, and CH4 production per gram soil carbon was two times greater from sites without permafrost than sites with permafrost. Maximum CH4 and median anaerobic CO2 production decreased with depth, while CO2:CH4 production increased with depth. Maximum CH4 production was highest in soils with herbaceous vegetation and soils that were either consistently or periodically inundated. This synthesis identifies the need to consider biome, landscape position, and vascular/moss vegetation types when modeling CH4 production in permafrost ecosystems and suggests the need for longer-term anaerobic incubations to fully capture CH4 dynamics. Our results demonstrate that as climate warms in arctic and boreal regions, rates of anaerobic CO2 and CH4 production will increase, not only as a result of increased temperature, but also from shifts in vegetation and increased

Spatio-temporal variability of lake CH4 fluxes and its influence on annual estimates

NASA Astrophysics Data System (ADS)

Natchimuthu, S.; Sundgren, I.; Gålfalk, M.; Klemedtsson, L.; Crill, P. M.; Danielsson, Å.; Bastviken, D.

2014-12-01

Lakes are major sources of methane (CH4) to the atmosphere and it has been shown that lakes contribute significantly to the global CH4 budget. However, the data behind these global estimates are snapshots in time and space only and they typically lack information on spatial and temporal variability of fluxes which can potentially lead to biased estimates. Recent studies have shown that diffusive flux, gas exchange velocity (k), ebullition and concentration of CH4 in the surface water can vary significantly in space within lakes. CH4 fluxes can also change at a broad range of temporal scales in response to seasons, temperature, lake mixing events, short term weather events like pressure variations, shifting winds and diel cycles. We sampled CH4 fluxes and surface water concentrations from three lakes of differing characteristics in southwest Sweden over two annual cycles, approximately every 14 days from April to October 2012 and from April to November 2013. CH4 fluxes were measured using floating chambers distributed in the lakes based on depth categories and dissolved CH4 concentrations were determined by a headspace equilibration method. We observed significant differences in CH4 concentration, diffusion, ebullition and total fluxes between and within the lakes. The fluxes increased exponentially with temperature in all three lakes and water temperature, for example, explained 53-78% of variations in total fluxes in the lakes. Based on our data which relied on improved spatial and temporal information, we demonstrate that measurements which do not take into account of the spatial variability in the lakes could substantially bias the whole lake estimates. For instance, in one of the lakes, measurements from the central parts of the lake represented only 58% of our estimates from all chambers on an average. In addition, we consider how intensive sampling in one season of the year may affect the annual estimates due to the complex interaction of temperature, air

A computational study of CH 4 storage in porous framework materials with metalated linkers: connecting the atomistic character of CH 4 binding sites to usable capacity

DOE PAGES

Tsivion, Ehud; Mason, Jarad A.; Gonzalez, Miguel. I.; ...

2016-03-29

In order to store natural gas (NG) inexpensively at adequate densities for use as a fuel in the transportation sector, new porous materials are being developed. Our work uses computational methods to explore strategies for improving the usable methane storage capacity of adsorbents, including metal-organic frameworks (MOFs), that feature open-metal sites incorporated into their structure by postsynthetic modification. The adsorption of CH 4 on several open-metal sites is studied by calculating geometries and adsorption energies and analyzing the relevant interaction factors. Approximate site-specific adsorption isotherms are obtained, and the open-metal site contribution to the overall CH 4 usable capacity ismore » evaluated. It is found that sufficient ionic character is required, as exemplified by the strong CH 4 affinities of 2,2'-bipyridine-CaCl 2 and Mg, Ca-catecholate. In addition, it is found that the capacity of a single metal site depends not only on its affinity but also on its geometry, where trigonal or "bent" low-coordinate exposed sites can accommodate three or four methane molecules, as exemplified by Ca-decorated nitrilotriacetic acid. The effect of residual solvent molecules at the open-metal site is also explored, with some positive conclusions. Not only can residual solvent stabilize the open-metal site, surprisingly, solvent molecules do not necessarily reduce CH 4 affinity, but can contribute to increased usable capacity by modifying adsorption interactions.« less

40 CFR 1065.660 - THC, NMHC, and CH4 determination.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 33 2014-07-01 2014-07-01 false THC, NMHC, and CH4 determination. 1065... POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calculations and Data Requirements § 1065.660 THC, NMHC, and CH4 determination. (a) THC determination and initial THC/CH 4 contamination corrections. (1) If we...

40 CFR 1065.660 - THC, NMHC, and CH4 determination.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 34 2012-07-01 2012-07-01 false THC, NMHC, and CH4 determination. 1065... POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calculations and Data Requirements § 1065.660 THC, NMHC, and CH4 determination. (a) THC determination and initial THC/CH 4 contamination corrections. (1) If we...

40 CFR 1065.660 - THC, NMHC, and CH4 determination.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 34 2013-07-01 2013-07-01 false THC, NMHC, and CH4 determination. 1065... POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calculations and Data Requirements § 1065.660 THC, NMHC, and CH4 determination. (a) THC determination and initial THC/CH 4 contamination corrections. (1) If we...

40 CFR 1065.660 - THC, NMHC, and CH4 determination.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 33 2011-07-01 2011-07-01 false THC, NMHC, and CH4 determination. 1065... POLLUTION CONTROLS ENGINE-TESTING PROCEDURES Calculations and Data Requirements § 1065.660 THC, NMHC, and CH4 determination. (a) THC determination and THC/CH 4 initial contamination corrections. (1) If we...

More CH4 is emitted during the fallow than during the growing season in a Mediterranean rice agrosystems

NASA Astrophysics Data System (ADS)

Martínez-Eixarch, Maite; Ibàñez, Carles; Alcaraz, Carles; Viñas, Marc; Aranda, Xavier; Saldaña, J. Antonio

2017-04-01

Paddy rice fields are an important source of greenhouse gas emissions (GHG) as they contribute 5 to 20 % of the global anthropogenic CH4 emissions. The Ebre Delta (Catalonia, NE Spain) is one of the most important wetland complexes in the Western Mediterranean with 65 % of its area covered by rice fields. The results herein presented assess the annual pattern of CH4 emissions from paddy rice in Ebre Delta, including the growing and fallow seasons as well as the major environmental variables modulating such emissions. Fifteen rice fields covering the geo-physical variability of the Ebre Delta were selected for GHG monitoring. Common agronomic management was practiced: water direct-seeding, permanent flooding and moderate mineral fertilization during the growing season and straw incorporation, progressive drainage of the fields after the harvest. Fields are left fallow during the winter. GHG were monthly sampled, from May to December in 2015. In each field, three closed chambers were used; from each of these, four gas samples were taken over a 30-minute period. Simultaneously, hydrological regime, soil physic-chemical parameters and plant cover were measured. GHG were analysed by gas chromatography. A Generalized linear model analysis (GLM) was performed to assess the most important influencing factors on CH4 emissions. An information-theoretic approach was used to find the best approximating models. Overall, the CH4 emissions showed a bi-modal pattern, with peaks in July-August and in October. Emissions rates ranged from 2.1 ± 0.5 to 7.5 ± 1.4 mg C-CH4 m-2 h-1 in the growing season (May to September) and from 25.0 ± 5.7 to 20.1 ± 3.3 mg C-CH4 m-2 h-1 at post-harvest (October to December). In total, 314 kg C-CH4 ha-1 were emitted from Ebre Delta rice fields, of which 70 % during post-harvest. Larger off-season emissions were likely induced by straw incorporation. The results of the GLM-IT analysis revealed that during the growing season, soil Eh and water level

Megafauna and frozen soil: the drivers of atmospheric CH4 dynamics

NASA Astrophysics Data System (ADS)

Zimov, N.; Zimov, S. A.

2010-12-01

During the last deglaciation (LD) a strong increase in atmospheric methane (CH4) concentrations occurred simultaneously with a rise in Greenland temperatures indicating that in the north, during this time period, strong CH4 sources “awakened”, as additionally documented by the appearance of a strong gradient between northern (Greenland) and southern (Antarctica) hemisphere atmospheric CH4 concentrations. This rise could not be caused by wetland expansion. A reconstruction of peatland formation dynamics has indicated that wetlands on Earth were few in LD and only actively expanded 10,000 yr BP, after atmospheric CH4 concentrations began to decline. Destabilization of methane clathrates also could not be the source for atmospheric CH4 increase. Geological CH4 (including methane clathrates) has the highest deuterium content (δD) among all of the known sources of CH4 while atmospheric CH4 δD values determined for the LD were record low. To explain recorded atmospheric CH4 and its isotopic dynamics required a strong northern source, which was active only during the LD and that provided very low δD CH4 values. Such a source is permafrost thawing under anaerobic conditions (or better stated soils of mammoth steppe-tundra ecosystems). Permafrost thawing is the strongest, among known, wetland sources (usually over 100g CH4/m2yr) and has a unique isotopic signature (δD = -400 per mil (-338 to -479 per mil), δ13C = -73 per mil (-58 to -99 per mil)). The main sources of atmospheric CH4 have different isotopic signatures (δ13C, δD). The isotopic content of atmospheric CH4 is a simple function of the weight average for all of the sources. Inclusion of permafrost source into a budget model of the atmospheric methane and its isotopes allowed us to reconstruct the dynamics of methane’s main sources. Model indicated geological source to be negligible as in LGM so and in LD and Holocene. During the glaciation, the largest methane source was megafauna, whose 1.4

Gas-Phase Synthesis and Characterization of CH4-Loaded Hydroquinone Clathrates

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, J.; Lee, Y; Takeya, S

2010-01-01

A CH{sub 4}-loaded hydroquinone (HQ) clathrate was synthesized via a gas-phase reaction using the {alpha}-form of crystalline HQ and CH{sub 4} gas at 12 MPa and room temperature. Solid-state {sup 13}C cross-polarization/magic angle spinning (CP/MAS) NMR and Raman spectroscopic measurements confirm the incorporation of CH{sub 4} molecules into the cages of the HQ clathrate framework. The chemical analysis indicates that about 69% of the cages are filled by CH{sub 4} molecules, that is, 0.69 CH{sub 4} per three HQ molecules. Rietveld refinement using synchrotron X-ray powder diffraction (XRD) data shows that the CH{sub 4}-loaded HQ clathrate adopts the {beta}-form ofmore » HQ clathrate in a hexagonal space group R3 with lattice parameters of a = 16.6191 {angstrom} and c = 5.5038 {angstrom}. Time-resolved synchrotron XRD and quadrupole mass spectroscopic measurements show that the CH{sub 4}-loaded HQ clathrate is stable up to 368 K and gradually transforms to the {alpha}-form by releasing the confined CH{sub 4} gases between 368-378 K. Using solid-state {sup 13}C CP/MAS NMR, the reaction kinetics between the {alpha}-form HQ and CH{sub 4} gas is qualitatively described in terms of the particle size of the crystalline HQ.« less

Scaled Hartree-Fock force field calculations for organothallium compounds: Normal-mode analysis for TlCH sub 3 Tl(CH sub 3 ) sub 2 sup + , Tl(CH sub 3 ) sub 3 , Tl(CH sub 3 ) sub 2 Br, and Tl(CH sub 3 ) sub 4 sup minus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schwerdtfeger, P.; Bowmaker, G.A.; Boyd, P.D.W.

1990-02-01

In a recent paper we presented Hartree-Fock (HF) calculations for aliphatic organothallium compounds. The diagonal HF force constants obtained from a Fletcher-Powell geometry optimization are now used for a normal-mode analysis of TlCH{sub 3}, Tl(CH{sub 3}){sub 2}{sup +}, Tl(CH{sub 3}){sub 3}, Tl(CH{sub 3}){sub 2}Br, and Tl(CH{sub 3}){sub 4}{sup {minus}}. In order to calculate frequencies comparable to experimental values, the HF force field has been scaled by using scaling factors obtained from experimental infrared and Raman measurements on Tl(CH{sub 3}){sub 2}{sup +} and TlBr. The vibrational spectra of Tl(CH{sub 3}){sub 2}{sup +} were remeasured (infrared and Raman) in order to obtainmore » an accurate force field. Predictions are made for the vibrational spectrum of the as yet undetected TlCH{sub 3} molecule. Experimental infrared and Raman results for Tl(CH{sub 3}){sub 3} compare reasonably well with our calculated frequencies. Relativistic and correlation effects are analyzed for the vibrational frequencies of Tl(CH{sub 3}){sub 2}{sup +}.« less

40 CFR Table C-2 to Subpart C - Default CH4 and N2O Emission Factors for Various Types of Fuel

Code of Federal Regulations, 2012 CFR

2012-07-01

... for Various Types of Fuel C Table C-2 to Subpart C Protection of Environment ENVIRONMENTAL PROTECTION... Combustion Sources Pt. 98, Subpt. C, Table C-2 Table C-2 to Subpart C—Default CH4 and N2O Emission Factors... factor (kg N2O/mmBtu) Coal and Coke (All fuel types in Table C-1) 1.1 × 10−02 1.6 × 10−03 Natural Gas 1.0...

40 CFR Table C-2 to Subpart C - Default CH4 and N2O Emission Factors for Various Types of Fuel

Code of Federal Regulations, 2011 CFR

2011-07-01

... for Various Types of Fuel C Table C-2 to Subpart C Protection of Environment ENVIRONMENTAL PROTECTION... Combustion Sources Pt. 98, Subpt. C, Table C-2 Table C-2 to Subpart C—Default CH4 and N2O Emission Factors... factor (kg N2O/mmBtu) Coal and Coke (All fuel types in Table C-1) 1.1 × 10−02 1.6 × 10−03 Natural Gas 1.0...

Was Early Mars Warmed by CH4?

NASA Astrophysics Data System (ADS)

Justh, H. L.; Kasting, J. F.

2001-12-01

Images from the Mariner, Viking and Mars Global Surveyor missions have shown geologic features on the Martian surface that seem to indicate an earlier period of hydrologic activity. Many researchers have suggested that the early Martian climate was more Earth-like with a Ts of 273 K or higher. The presence of liquid water would require a greenhouse effect much larger than needed at present since S0 is 25% lower 3.8 billion years ago when the channels are thought to have formed. Research into the effects of CO2 clouds upon the climate of early Mars have yielded results that would not effectively warm the surface to the temperature needed to account for the presence of liquid water. Forget and Pierrehumbert (Science, 1997) showed that large crystals of CO2 ice in clouds that form in the upper troposphere would produce a strong warming effect. Obtaining mean surface temperatures above 273 K would require 100% cloud cover, a condition that is unrealistic for early Mars. It has also been shown that any reduction in cloud cover makes it difficult to achieve warm Martian surface temperatures except at high pressures. CO2 clouds could also cool the Martian surface if they were low and optically thick. CO2 ice may be hard to nucleate, leading to the formation of very large particles (Glandorf, private communication). CH4 has been suggested as an important greenhouse gas on the early Earth. This has led us to look at CH4 as a potential solution to the early Mars climate issue. To investigate the possible warming effect of CH4, we utilized a modified, one-dimensional, radiative-convective climate model that has been used in previous studies of the early Martian climate. New calculations of the effects of CH4 upon the early Martian climate will be presented. The use of CH4 to warm the surface of early Mars does not necessarily imply the presence of life on Mars. Abiotic sources of CH4, such as serpentinization of ultramafic rocks, could supply the concentrations needed to warm

Arctic tundra and mountain landscapes are persistent sinks of atmospheric CH4

NASA Astrophysics Data System (ADS)

Christiansen, Jesper; Winkler, Renato; Juncher Jørgensen, Christian

2017-04-01

Recent studies have shown significant rates of net uptake of atmospheric methane (CH4) in Arctic tundra soils. Oxidation of CH4 in these cold, dry soils in the Arctic region can counteract CH4 emissions from wetlands and play a potential important role for the net Arctic CH4 budget. However, significant knowledge gaps exist on the overall magnitude of the net CH4 sink in these cold, dry systems as the spatial and environmental limits for CH4 oxidation has not been determined. In particular, the extent, magnitude and drivers of CH4 oxidation in mountains and alpine landforms, which occupy large land areas in the Arctic and High Arctic has not yet been investigated leaving a potential vast CH4 sink unquantified with major potential implications for our conceptual view of Arctic CH4 budget in a changing climate. Here we present the results from two expeditions in the summers of 2015 and 2016 from Disko Bay and in the pro-glacial landscape in vicinity of the Russell Glacier, Kangerlussuaq, Greenland, respectively. The aim of our work is to determine the magnitude and extent of net uptake of atmospheric CH4 across a variety of previously unexplored dry tundra and post-glacial landforms in the Arctic, i.e. marginal moraines and other glacial features at the Greenland ice sheet as well as mountain tops and outwash plains. We used high-precision, mobile cavity-ring-down spectrometers (e.g. model G4301 GasScouter, Picarro Inc.) to achieve reliable flux estimates in sub-ambient CH4 concentration levels with a 4-minute enclosure time per chamber measurement. Our results show a persistent net uptake of CH4 uptake in these dry, extreme environments that rival the sink strength observed in temperate forest soils, otherwise considered the primary global terrestrial sink of atmospheric CH4. In this dynamic glacial landscape the magnitude of the net CH4 uptake is mainly constrained by recent landscape evolution along glacier margins and meltwater systems. Utilizing the high

Climate change reduces the net sink of CH4 and N2O in a semiarid grassland.

PubMed

Dijkstra, Feike A; Morgan, Jack A; Follett, Ronald F; Lecain, Daniel R

2013-06-01

Atmospheric concentrations of methane (CH4 ) and nitrous oxide (N2 O) have increased over the last 150 years because of human activity. Soils are important sources and sinks of both potent greenhouse gases where their production and consumption are largely regulated by biological processes. Climate change could alter these processes thereby affecting both rate and direction of their exchange with the atmosphere. We examined how a rise in atmospheric CO2 and temperature affected CH4 and N2 O fluxes in a well-drained upland soil (volumetric water content ranging between 6% and 23%) in a semiarid grassland during five growing seasons. We hypothesized that responses of CH4 and N2 O fluxes to elevated CO2 and warming would be driven primarily by treatment effects on soil moisture. Previously we showed that elevated CO2 increased and warming decreased soil moisture in this grassland. We therefore expected that elevated CO2 and warming would have opposing effects on CH4 and N2 O fluxes. Methane was taken up throughout the growing season in all 5 years. A bell-shaped relationship was observed with soil moisture with highest CH4 uptake at intermediate soil moisture. Both N2 O emission and uptake occurred at our site with some years showing cumulative N2 O emission and other years showing cumulative N2 O uptake. Nitrous oxide exchange switched from net uptake to net emission with increasing soil moisture. In contrast to our hypothesis, both elevated CO2 and warming reduced the sink of CH4 and N2 O expressed in CO2 equivalents (across 5 years by 7% and 11% for elevated CO2 and warming respectively) suggesting that soil moisture changes were not solely responsible for this reduction. We conclude that in a future climate this semiarid grassland may become a smaller sink for atmospheric CH4 and N2 O expressed in CO2 -equivalents. © 2013 Blackwell Publishing Ltd.

Hydrothermal plumes in the Gulf of Aden, as characterized by light transmission, Mn, Fe, CH4 and δ13C-CH4 anomalies

NASA Astrophysics Data System (ADS)

Gamo, Toshitaka; Okamura, Kei; Hatanaka, Hiroshi; Hasumoto, Hiroshi; Komatsu, Daisuke; Chinen, Masakazu; Mori, Mutsumi; Tanaka, Junya; Hirota, Akinari; Tsunogai, Urumu; Tamaki, Kensaku

2015-11-01

We conducted water column surveys to search for hydrothermal plumes over the spreading axes in the Gulf of Aden between 45°35‧E and 52°42‧E. We measured light transmission and chemical tracers Mn, Fe, CH4 and δ13C of CH4 in seawater taken using a CTD-Carrousel multi-sampling system at 12 locations including a control station in the Arabian Sea. We recognized three types of hydrothermal plumes at depths of 650 to 900 m (shallow plumes), 1000 to 1200 m (intermediate plumes), and >1500 m (deep plumes). The shallow plumes were apparently originated from newly discovered twin seamounts (12°03-06‧N and 45°35-41‧E) at the westernmost survey area, where two-dimensional distributions of light transmission and Mn were mapped by tow-yo observations of the CTD-sampling system with an in situ auto-analyzer GAMOS. The maximum concentrations of Mn, Fe, and CH4 of 46 nM, 251 nM, and 15 nM, respectively, were observed for collected seawater within the shallow plumes. The intermediate plumes were characterized by anomalies of light transmission, Mn, Fe, and δ13C of CH4, but by little CH4 anomalies, suggesting that CH4 had been consumed down to the background level during the aging of the plumes. Anomalies of δ3He already reported by the World Ocean Circulation Experiment (WOCE) program exhibited a hydrothermal plume-like peak at 2000 m depth in the Gulf of Aden, which seems to coincide with the deep plumes observed in this study. The endmember δ13C-CH4 values for the shallow and the deep plumes were estimated to be in a range between -10‰ and -15‰, demonstrating that the sources of CH4 are not biogenic but magmatic as similarly observed at sediment-starved mid-oceanic ridges.

ChIP-nexus: a novel ChIP-exo protocol for improved detection of in vivo transcription factor binding footprints

PubMed Central

He, Qiye; Johnston, Jeff; Zeitlinger, Julia

2014-01-01

Understanding how eukaryotic enhancers are bound and regulated by specific combinations of transcription factors is still a major challenge. To better map transcription factor binding genome-wide at nucleotide resolution in vivo, we have developed a robust ChIP-exo protocol called ChIP experiments with nucleotide resolution through exonuclease, unique barcode and single ligation (ChIP-nexus), which utilizes an efficient DNA self-circularization step during library preparation. Application of ChIP-nexus to four proteins—human TBP and Drosophila NFkB, Twist and Max— demonstrates that it outperforms existing ChIP protocols in resolution and specificity, pinpoints relevant binding sites within enhancers containing multiple binding motifs and allows the analysis of in vivo binding specificities. Notably, we show that Max frequently interacts with DNA sequences next to its motif, and that this binding pattern correlates with local DNA sequence features such as DNA shape. ChIP-nexus will be broadly applicable to studying in vivo transcription factor binding specificity and its relationship to cis-regulatory changes in humans and model organisms. PMID:25751057

Theoretical study on the reaction mechanism of CH 4 with CaO

NASA Astrophysics Data System (ADS)

Yang, Hua-Qing; Hu, Chang-Wei; Qin, Song

2006-11-01

The reaction pathways and energetics for the reaction of methane with CaO are discussed on the singlet spin state potential energy surface at the B3LYP/6-311+G(2df,2p) and QCISD/6-311++G(3df,3pd)//B3LYP/6-311+G(2df,2p) levels of theory. The reaction of methane with CaO is proposed to proceed in the following reaction pathways: CaO + CH 4 → CaOCH 4 → [TS] → CaOH + CH 3, CaO + CH 4 → OCaCH 4 → [TS] → HOCaCH 3 → CaOH + CH 3 or [TS] → CaCH 3OH → Ca + CH 3OH, and OCaCH 4 → [TS] → HCaOCH 3 → CaOCH 3 + H or [TS] → CaCH 3OH → Ca + CH 3OH. The gas-phase methane-methanol conversion by CaO is suggested to proceed via two kinds of important reaction intermediates, HOCaCH 3 and HCaOCH 3, and the reaction pathway via the hydroxy intermediate (HOCaCH 3) is energetically more favorable than the other one via the methoxy intermediate (HCaOCH 3). The hydroxy intermediate HOCaCH 3 is predicted to be the energetically most preferred configuration in the reaction of CaO + CH 4. Meanwhile, these three product channels (CaOH + CH 3, CaOCH 3 + H and Ca + CH 3OH) are expected to compete with each other, and the formation of methyl radical is the most preferable pathway energetically. On the other hand, the intermediates HCaOCH 3 and HOCaCH 3 are predicted to be the energetically preferred configuration in the reaction of Ca + CH 3OH, which is precisely the reverse reaction of methane hydroxylation.

Experimental warming of a mountain tundra increases soil CO2 effluxes and enhances CH4 and N2O uptake at Changbai Mountain, China

PubMed Central

Zhou, Yumei; Hagedorn, Frank; Zhou, Chunliang; Jiang, Xiaojie; Wang, Xiuxiu; Li, Mai-He

2016-01-01

Climatic warming is expected to particularly alter greenhouse gas (GHG) emissions from soils in cold ecosystems such as tundra. We used 1 m2 open-top chambers (OTCs) during three growing seasons to examine how warming (+0.8–1.2 °C) affects the fluxes of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) from alpine tundra soils. Results showed that OTC warming increased soil CO2 efflux by 141% in the first growing season and by 45% in the second and third growing season. The mean CH4 flux of the three growing seasons was −27.6 and −16.7 μg CH4-C m−2h−1 in the warmed and control treatment, respectively. Fluxes of N2O switched between net uptake and emission. Warming didn’t significantly affect N2O emission during the first and the second growing season, but stimulated N2O uptake in the third growing season. The global warming potential of GHG was clearly dominated by soil CO2 effluxes (>99%) and was increased by the OTC warming. In conclusion, soil temperature is the main controlling factor for soil respiration in this tundra. Climate warming will lead to higher soil CO2 emissions but also to an enhanced CH4 uptake with an overall increase of the global warming potential for tundra. PMID:26880107

Vibrational dynamics of aniline(Ar)1 and aniline(CH4)1 clusters

NASA Astrophysics Data System (ADS)

Nimlos, M. R.; Young, M. A.; Bernstein, E. R.; Kelley, D. F.

1989-11-01

The first excited electronic state (S1) vibrational dynamics of aniline(Ar)1 and aniline(CH4)1 van der Waals (vdW) clusters have been studied using molecular jet and time resolved emission spectroscopic techniques. The rates of intramolecular vibrational energy redistribution (IVR) and vibrational predissociation (VP) as functions of vibrational energy are reported for both clusters. For vibrational energy in excess of the cluster binding energy, both clusters are observed to dissociate. The dispersed emission spectra of these clusters demonstrate that aniline(Ar)1 dissociates to all energetically accessible bare molecule states and that aniline(CH4)1 dissociates selectively to only the bare molecule vibrationless state. The emission kinetics show that in the aniline(Ar)1 case, the initially excited states have nanosecond lifetimes, and intermediate cluster states have very short lifetimes. In contrast, the initially excited aniline(CH4)1 states and other intermediate vibrationally excited cluster states are very short lived (<100 ps), and the intermediate cluster 00 state is observed. These results can be understood semiquantitatively in terms of an overall serial IVR/VP mechanism which consists of the following: (1) the rates of chromophore to vdW mode IVR are given by Fermi's golden rule, and the density of vdW vibrational states is the most important factor in determining the relative [aniline(Ar)1 vs aniline(CH4)1] rates of IVR; (2) IVR among the vdW modes is rapid; and (3) VP rates can be calculated by a restricted vdW mode phase space Rice-Ramsberger-Kassel-Marcus theory. Since the density of vdW states is three orders of magnitude greater for aniline(CH4)1 than aniline(Ar)1 at 700 cm-1, the model predicts that IVR is slow and rate limiting in aniline(Ar)1, whereas VP is slow and rate limiting in aniline(CH4)1. The agreement of these predictions with the experimental results is very good and is discussed in detail.

Carbon isotope exchange in the system CO 2-CH 4 at elevated temperatures

NASA Astrophysics Data System (ADS)

Horita, Juske

2001-06-01

Carbon isotope exchange was investigated for the system CO 2-CH 4 at 150 to 600°C in the presence of several potential catalysts by use of isotopically normal or 13C-enriched gases. Silica gel, graphite, molecular sieve Linde 4A, magnetite, and hematite oxidized small amounts of CH 4 in starting CO 2-CH 4 mixtures to CO and CO 2 but failed to enhance the net rate of carbon isotope exchange between CO 2 and CH 4, even after 169 to 1833 h at 400 to 500°C. In contrast, several commercial transition-metal catalysts (Ni, Pd, Rh, and Pt) promoted reactions significantly toward chemical and isotopic equilibrium. With the Ni catalyst, the attainment of carbon isotopic equilibrium between CO 2 and CH 4 was demonstrated for the first time at temperatures from 200 to 600°C by complete isotopic reversal from opposite directions. The experimentally determined carbon isotope fractionation factors between CO 2 and CH 4 (10 3lnα) were similar to, but slightly greater than (0.7-1.1‰, 0.89‰ on average), those of statistical-mechanical calculations by Richet et al. (1977). The experimental results can be described by the following equation between 200 and 600°C only: 10 3lnα(CO 2-CH 4) = 26.70 - 49.137(10 3/T) + 40.828(10 6/T 2) - 7.512(10 9/T 3) (T = 473.15-873.15 K, 1σ = ±0.14‰, n = 44). Alternatively, an equation generated by fitting Richet et al. (1977) data in the temperature range from 0 to 1300°C can be modified by adding +0.89‰ to its constant; 10 3lnα(CO 2-CH 4) = 0.16 + 11.754(10 6/T 2) - 2.3655(10 9/T 3) + 0.2054(10 12/T 4) (T = 273-1573 K, 1σ = ±0.21‰, n = 44). This and other recent experimental studies in the literature demonstrate that transition metals, which are widespread in many natural materials, can catalyze reactions among natural gases at relatively low temperatures (≤200°C). The role of natural catalysts, "geocatalysts," in the abiogenic formation of methane, hydrocarbons, and simple organic compounds has important implications, ranging

Response of CH4 emissions to straw and biochar applications in double-rice cropping systems: Insights from observations and modeling.

PubMed

Chen, Dan; Wang, Cong; Shen, Jianlin; Li, Yong; Wu, Jinshui

2018-04-01

Paddy soil plays an essential role in contributing to the emission of methane (CH 4 ), a potent greenhouse gas, to the atmosphere. This study aimed to demonstrate the effects of straw incorporation and straw-derived biochar amendment on CH 4 emissions from double-rice cropping fields and to explore their potential mechanisms based on in-situ field measurements conducted for a period of three years (2012-2014) and model analysis. The results showed that the improved soil aeration due to biochar amendment resulted in low CH 4 emissions and that sufficient substrate carbon availability in straw amendment treatments caused high CH 4 emissions. The newly developed CH 4 emission module for the water and nitrogen management model (WNMM), a process-based biophysical model, performed well when simulating both daily CH 4 fluxes and the annual cumulative CH 4 emissions under straw incorporation and biochar amendment. Results of our study indicate that the model has a great potential for upscaling and could benefit mechanism analyses about the factors regulating CH 4 emissions. Application of biochar into paddy fields provides a great opportunity to reduce CH 4 emissions, and the decrease in CH 4 emissions following biochar amendment with repeated crop cycles would sustain for a prolonged period. Copyright © 2017 Elsevier Ltd. All rights reserved.

WETTING STIMULATES ATMOSPHERIC CH4 OXIDATION BY ALPINE SOIL (R823442)

EPA Science Inventory

Studies were done to assess the effects of soil moisture manipulations on CH₄ oxidation in soils from a dry alpine tundra site. When water was added to these soils there was a stimulation of CH₄ oxidation. This stimulation of CH₄ oxidation took ti...

Understanding the Temporal Variation of CO2 and CH4 Fluxes in a Subtropical Seasonal Wetland

NASA Astrophysics Data System (ADS)

Gomez-Casanovas, N.; DeLucia, N.; DeLucia, E. H.; Boughton, E.; Bernacchi, C.

2017-12-01

experience more frequent floods and droughts as well as higher temperatures, conditions that will likely alter ecosystem attributes such as GPP. Our results indicate that CH4 emissions from subtropical wetlands will likely respond to projected changes in precipitation, temperature and productivity, substantially affecting the net GHG sink strength of these systems in future climate scenarios.

Early Mars serpentinization-derived CH4 reservoirs, H2 induced warming and paleopressure evolution

NASA Astrophysics Data System (ADS)

Lasue, J.; Chassefiere, E.; Langlais, B.; Quesnel, Y.

2016-12-01

CH4 has been observed on Mars both by remote sensing and in situ during the past 15 years. Early Mars serpentinization is one possible abiotic mechanism that could not only produce methane, but also explain the observed Martian remanent magnetic field. Assuming a cold early Mars, a cryosphere could trap such CH4 as clathrates in stable form at depth. We recently estimated the maximum storage capacity of such clathrate layer to be about 2x1019 to 2x1020 moles of methane. Such reservoirs may be stable or unstable, depending on many factors that are poorly constrained: major and sudden geological events such as the Tharsis bulge formation, the Hellas impact or the martian polar wander, could have destabilized the clathrates early in the history of the planet and released large quantities of gas in the atmosphere. Here we estimate the associated amounts of serpentinization-derived CH4 stored in the cryosphere that have been released to the atmosphere at the end of the Noachian and the beginning of the Hesperian. Due to rapid clathrate dissociation and photochemical conversion of CH4 to H2, these episodes of massive CH4 release may have resulted in transient H2-rich atmospheres, at typical levels of 10-20% in a background 1-2 bar CO2 atmosphere. We propose that the early Mars cryosphere had a sufficient CH4 storage capacity to have maintained H2-rich transient atmospheres during a total time period up to several Myr or tens of Myr, having potentially contributed - by collision-induced heating effect of atmospheric H2 - to the formation of valley networks during the late Noachian and early Hesperian.

Coupled potential energy surface for the F(2P)+CH4→HF+CH3 entrance channel and quantum dynamics of the CH4·F- photodetachment.

PubMed

Westermann, Till; Eisfeld, Wolfgang; Manthe, Uwe

2013-07-07

An approach to construct vibronically and spin-orbit coupled diabatic potential energy surfaces (PESs) which describe all three relevant electronic states in the entrance channels of the X(P) + CH4 →HX + CH3 reactions (with X=F((2)P), Cl((2)P), or O((3)P)) is introduced. The diabatization relies on the permutational symmetry present in the methane molecule and results in diabatic states which transform as the three p orbitals of the X atom. Spin-orbit coupling is easily and accurately included using the atomic spin-orbit coupling matrix of the isolated X atom. The method is applied to the F + CH4 system obtaining an accurate PES for the entrance channel based on ab initio multi-reference configuration interaction (MRCI) calculations. Comparing the resulting PESs with spin-orbit MRCI calculations, excellent agreement is found for the excited electronic states at all relevant geometries. The photodetachment spectrum of CH4·F(-) is investigated via full-dimensional (12D) quantum dynamics calculations on the coupled PESs using the multi-layer multi-configurational time-dependent Hartree approach. Extending previous work [J. Palma and U. Manthe, J. Chem. Phys. 137, 044306 (2012)], which was restricted to the dynamics on a single adiabatic PES, the contributions of the electronically excited states to the photodetachment spectrum are calculated and compared to experiment. Considering different experimental setups, good agreement between experiment and theory is found. Addressing questions raised in the previous work, the present dynamical calculations show that the main contribution to the second peak in the photodetachment spectrum results from electron detachment into the electronically excited states of the CH4F complex.

Above- and belowground fluxes of CH4 from boreal shrubs and Scots pine

NASA Astrophysics Data System (ADS)

Halmeenmäki, Elisa; Heinonsalo, Jussi; Santalahti, Minna; Putkinen, Anuliina; Fritze, Hannu; Pihlatie, Mari

2016-04-01

Boreal upland forests are considered as an important sink for the greenhouse gas methane (CH4) due to CH4 oxidizing microbes in the soil. However, recent evidence suggests that vegetation can act as a significant source of CH4. Also, preliminary measurements indicate occasional emissions of CH4 above the tree canopies of a boreal forest. Nevertheless, the sources and the mechanisms of the observed CH4 emissions are still mostly unknown. Furthermore, the majority of CH4 flux studies have been conducted with the soil chamber method, thus not considering the role of the vegetation itself. We conducted a laboratory experiment to study separately the above- and belowground CH4 fluxes of bilberry (Vaccinium myrtillus), lingonberry (Vaccinium vitis-idaea), heather (Calluna vulgaris), and Scots pine (Pinus sylvestris), which were grown in microcosms. The above- and belowground fluxes of the plants were measured separately, and these fluxes were compared to fluxes of microcosms containing only humus soil. In addition to the flux measurements, we analysed the CH4 producing archaea (methanogens) and the CH4 consuming bacteria (methanotrophs) with the qPCR method to discover whether these microbes contribute to the CH4 exchange from the plant material and the soil. The results of the flux measurements indicate that the humus soil with roots of lingonberry, heather, and Scots pine consume CH4 compared to bare humus soil. Simultaneously, the shoots of heather and Scots pine emit small amounts of CH4. We did not find detectable amounts of methanogens from any of the samples, suggesting the produced CH4 could be of non-microbial origin, or produced by very small population of methanogens. Based on the first preliminary results, methanotrophs were present in all the studied plant species, and especially in high amounts in the rooted soils, thus implying that the methanotrophs could be responsible of the CH4 uptake in the root-soil systems.

Macromolecule simulation and CH4 adsorption mechanism of coal vitrinite

NASA Astrophysics Data System (ADS)

Yu, Song; Yan-ming, Zhu; Wu, Li

2017-02-01

The microscopic mechanism of interactions between CH4 and coal macromolecules is of significant practical and theoretical importance in CBM development and methane storage. Under periodic boundary conditions, the optimal energy configuration of coal vitrinite, which has a higher torsion degree and tighter arrangement, can be determined by the calculation of molecular mechanics (MM) and molecular dynamics (MD), and annealing kinetics simulation based on ultimate analysis, 13C NMR, FT IR and HRTEM. Macromolecular stabilization is primarily due to the van der Waals energy and covalent bond energy, mainly consisting of bond torsion energy and bond angle energy. Using the optimal configuration as the adsorbent, GCMC simulation of vitrinite adsorption of CH4 is conducted. A saturated state is reached after absorbing 17 CH4s per coal vitrinite molecule. CH4 is preferentially adsorbed on the edge, and inclined to gathering around the branched chains of the inner vitrinite sites. Finally, the adsorption parameters are calculated through first principle DFT. The adsorbability order is as follows: aromatic structure> heteroatom rings > oxygen functional groups. The adsorption energy order is as follows: Top < Bond < Center, Up < Down. The order of average RDF better reflects the adsorption ability and that of [-COOH] is lower than those of [sbnd Cdbnd O] and [Csbnd Osbnd C]. CH4 distributed in the distance of 0.99-16 Å to functional groups in the type of monolayer adsorption and the average distance order manifest as [sbnd Cdbnd O] (1.64 Å) < [Csbnd Osbnd C] (1.89 Å) < [sbnd COOH] (3.78 Å) < [-CH3] (4.11 Å) according to the average RDF curves. CH4 enriches around [sbnd Cdbnd O] and [Csbnd O-C] whereas is rather dispersed about [-COOH] and [CH3]. Simulation and experiment data are both in strong agreement with the Langmuir and D-A isothermal adsorption model and the D-A model fit better than Langmuir model. Preferential adsorption sites and orientations in vitrinite are

Satellite Boreal Measurements over Alaska and Canada During June-July 2004: Simultaneous Measurements of Upper Tropospheric CO, C2H6, HCN, CH3Cl, CH4, C2H2, CH2OH, HCOOH, OCS, and SF6 Mixing Ratios

NASA Technical Reports Server (NTRS)

Rinsland, Curtis P.; Dufour, Gaelle; Boone, Chris D.; Bernath, Peter F.; Chiou, Linda; Coheur, Pierre-Francois; Turquety, Solene; Clerbaux, Cathy

2007-01-01

Simultaneous ACE (Atmospheric Chemistry Experiment) upper tropospheric CO, C2H6, HCN, CH3Cl, CH4 , C2H2 , CH30H, HCOOH, and OCS measurements show plumes up to 185 ppbv (10 (exp -9) per unit volume) for CO, 1.36 ppbv for C2H6, 755 pptv (10(exp -12) per unit volume) for HCN, 1.12 ppbv for CH3C1, 1.82 ppmv, (10(exp -6) per unit volume) for CH4, 0.178 ppbv for C2H2, 3.89 ppbv for CH30H, 0.843 ppbv for HCOOH, and 0.48 ppbv for OCS in western Canada and Alaska at 50 deg N-68 deg N latitude between 29 June and 23 July 2004. Enhancement ratios and emission factors for HCOOH, CH30H, HCN, C2H6, and OCS relative to CO at 250-350 hPa are inferred from measurements of young plumes compared with lower mixing ratios assumed to represent background conditions based on a CO emission factor derived from boreal measurements. Results are generally consistent with the limited data reported for various vegetative types and emission phases measured in extratropical forests including boreal forests. The low correlation between fire product emission mixing ratios and the S176 mixing ratio is consistent with no significant SF6 emissions from the biomass fires.

40 CFR Table Aa-2 to Subpart Aa of... - Kraft Lime Kiln and Calciner Emissions Factors for CH4 and N2O

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Kraft Lime Kiln and Calciner Emissions Factors for CH4 and N2O AA Table AA-2 to Subpart AA of Part 98 Protection of Environment ENVIRONMENTAL... Manufacturing Pt. 98, Subpt. AA, Table AA -2 Table AA-2 to Subpart AA of Part 98—Kraft Lime Kiln and Calciner...

Characterizing CH4 and N2O emissions from an intensive dairy operation in summer and fall in China

NASA Astrophysics Data System (ADS)

Zhu, Gaodi; Ma, Xiaoyuan; Gao, Zhiling; Ma, Wenqi; Li, Jianguo; Cai, Zhenjiang

2014-02-01

Evaluation of the global warming potential of the dairy industry both in China and globally necessitates reliable characterization of CH4 and N2O emissions. However, CH4 and N2O emissions from dairy operations differ with feeds, herd structures and manure management practices, and the lack of N2O and CH4 emission measurements for China, especially for intensive dairy operations, causes substantial uncertainty in accounting for GHGs from dairy operation both in China and globally. In this study, CH4 and N2O emissions during summer to fall period from an intensive feedlot in China were characterized to fill the data gap. The diurnal CH4 emission patterns for milking cows and heifers were driven by the feeding activities and the diurnal N2O patterns by the diurnal changes in temperature. The CH4 emission rates of 397 g head-1 d-1 (23.63 L CH4 kg-1 milk) (in summer) and 279 g head-1 d-1 (in fall) for milking cows and heifers accounted for 5.17% and 7.68% of their daily gross energy intakes, whereas the N2O emission rates of 36.7 g head-1 d-1 (0.85 L N2O kg-1 milk) for milking cows and 24.2 g head-1 d-1 for heifers accounted for 4.25% and 6.86% of the daily feed N intake. The CH4 conversion factor and CH4 emission intensity in the measurement season for intensive dairy operations in China are lower than those for collective operations in China, and the CH4 emission intensity is similar to those in developed countries.

Stringent upper limit of CH4 on Mars based on SOFIA/EXES observations

NASA Astrophysics Data System (ADS)

Aoki, S.; Richter, M. J.; DeWitt, C.; Boogert, A.; Encrenaz, T.; Sagawa, H.; Nakagawa, H.; Vandaele, A. C.; Giuranna, M.; Greathouse, T. K.; Fouchet, T.; Geminale, A.; Sindoni, G.; McKelvey, M.; Case, M.; Kasaba, Y.

2018-03-01

Discovery of CH4 in the Martian atmosphere has led to much discussion since it could be a signature of biological and/or geological activities on Mars. However, the presence of CH4 and its temporal and spatial variations are still under discussion because of the large uncertainties embedded in the previous observations. We performed sensitive measurements of Martian CH4 by using the Echelon-Cross-Echelle Spectrograph (EXES) onboard the Stratospheric Observatory for Infrared Astronomy (SOFIA) on 16 March 2016, which corresponds to summer (Ls = 123.2∘) in the northern hemisphere on Mars. The high altitude of SOFIA ( 13.7 km) enables us to significantly reduce the effects of terrestrial atmosphere. Thanks to this, SOFIA/EXES improves our chances of detecting Martian CH4 lines because it reduces the impact of telluric CH4 on Martian CH4, and allows us to use CH4 lines in the 7.5 μm band which has less contamination. However, our results show no unambiguous detection of Martian CH4. The Martian disk was spatially resolved into 3 × 3 areas, and the upper limits on the CH4 volume mixing ratio range from 1 to 9 ppb across the Martian atmosphere, which is significantly less than detections in several other studies. These results emphasize that release of CH4 on Mars is sporadic and/or localized if the process is present.

Environmental and vegetation controls on the spatial variability of CH4 emission from wet-sedge and tussock tundra ecosystems in the Arctic.

PubMed

McEwing, Katherine Rose; Fisher, James Paul; Zona, Donatella

Despite multiple studies investigating the environmental controls on CH 4 fluxes from arctic tundra ecosystems, the high spatial variability of CH 4 emissions is not fully understood. This makes the upscaling of CH 4 fluxes from plot to regional scale, particularly challenging. The goal of this study is to refine our knowledge of the spatial variability and controls on CH 4 emission from tundra ecosystems. CH 4 fluxes were measured in four sites across a variety of wet-sedge and tussock tundra ecosystems in Alaska using chambers and a Los Gatos CO 2 and CH 4 gas analyser. All sites were found to be sources of CH 4 , with northern sites (in Barrow) showing similar CH 4 emission rates to the southernmost site (ca. 300 km south, Ivotuk). Gross primary productivity (GPP), water level and soil temperature were the most important environmental controls on CH 4 emission. Greater vascular plant cover was linked with higher CH 4 emission, but this increased emission with increased vascular plant cover was much higher (86 %) in the drier sites, than the wettest sites (30 %), suggesting that transport and/or substrate availability were crucial limiting factors for CH 4 emission in these tundra ecosystems. Overall, this study provides an increased understanding of the fine scale spatial controls on CH 4 flux, in particular the key role that plant cover and GPP play in enhancing CH 4 emissions from tundra soils.

Consistent regional fluxes of CH4 and CO2 inferred from GOSAT proxy XCH4 : XCO2 retrievals, 2010-2014

NASA Astrophysics Data System (ADS)

Feng, Liang; Palmer, Paul I.; Bösch, Hartmut; Parker, Robert J.; Webb, Alex J.; Correia, Caio S. C.; Deutscher, Nicholas M.; Domingues, Lucas G.; Feist, Dietrich G.; Gatti, Luciana V.; Gloor, Emanuel; Hase, Frank; Kivi, Rigel; Liu, Yi; Miller, John B.; Morino, Isamu; Sussmann, Ralf; Strong, Kimberly; Uchino, Osamu; Wang, Jing; Zahn, Andreas

2017-04-01

South America. We find no evidence from GOSAT that tropical South American CH4 fluxes were dramatically affected by the two large-scale Amazon droughts. However, we find that GOSAT data are consistent with double seasonal peaks in Amazonian fluxes that are reproduced over the 5 years we studied: a small peak from January to April and a larger peak from June to October, which are likely due to superimposed emissions from different geographical regions.

Fluxes of CH4 and CO2 from soil and termite mounds in south Sudanian savanna of Burkina Faso (West Africa)

NASA Astrophysics Data System (ADS)

Brümmer, Christian; Papen, Hans; Wassmann, Reiner; Brüggemann, Nicolas

2009-03-01

The contribution of West African savanna ecosystems to global greenhouse gas budgets is highly uncertain. In this study we quantified soil-atmosphere CH4 and CO2 fluxes in the southwest of Burkina Faso from June to September 2005 and from April to September 2006 at four different agricultural fields planted with sorghum (n = 2), cotton, and peanut and at a natural savanna site with termite (Cubitermes fungifaber) mounds. During the rainy season both CH4 uptake and CH4 emission were observed in the savanna, which was on average a CH4 source of 2.79 and 2.28 kg CH4-C ha-1 a-1 in 2005 and 2006, respectively. The crop sites were an average CH4 sink of -0.67 and -0.70 kg CH4-C ha-1 a-1 in the 2 years, without significant seasonal variation. Mean annual soil respiration ranged between 3.86 and 5.82 t CO2-C ha-1 a-1 in the savanna and between 2.50 and 4.51 t CO2-C ha-1 a-1 at the crop sites. CH4 emission from termite mounds was 2 orders of magnitude higher than soil CH4 emissions, whereas termite CO2 emissions were of the same order of magnitude as soil CO2 emissions. Termite CH4 and CO2 release in the savanna contributed 8.8% and 0.4% to the total soil CH4 and CO2 emissions, respectively. At the crop sites, where termite mounds had been almost completely removed because of land use change, termite fluxes were insignificant. Mound density-based upscaling of termite CH4 fluxes resulted in a global termite CH4 source of 0.9 Tg a-1, which corresponds to 0.15% of the total global CH4 budget of 582 Tg a-1, hence significantly lower than those obtained previously by biomass-based calculations. This study emphasizes that land use change, which is of high relevance in this region, has particularly affected soil CH4 fluxes in the past and might still do so in the future.

Geographic Inventory Framework (GiF) for estimating N2O and CH4 emissions from agriculture in the province of Alberta, Canada

NASA Astrophysics Data System (ADS)

Dimitrov, D. D.; Wang, J.

2016-12-01

A Geographic Information Framework (GiF) has been created to estimate and map agricultural N2O and CH4 emissions of the province of Alberta, Canada. The GiF consists of a modelling component, a GIS component, and application software to communicate between the model, database and census data. For compatibility, GiF follows the IPCC Tier 1 method and contains census data for animal populations, crop areas, and farms for the main IPCC animal and plant types (dairy cows, cattle cows, pigs, sheep, poultry, other animals, grasses, legumes, other crops), and estimated N2O and CH4 emissions from manure management, enteric fermentation, direct soil emissions (with applied manure, synthetic fertilizer, crop residue degradation, biological fixation) and indirect soil emissions (with atmospheric deposition and leaching). Methane emissions from enteric fermentation (609.24 Gg) prevailed over those from manure (44.99 Gg), and nitrous oxide emission from manure (22.01 Gg) prevailed over those from soil (17.73 Gg), with cattle cows emitting most N2O and CH4, followed by plant N2O emissions, and pigs and dairy cows CH4 emissions. The GIS maps showed discernible pattern of N2O and CH4 emissions increasing from North and West to the central Alberta and then slightly declining to South and East, which could be useful to address various mitigation strategies. The framework allows easy replacement of Tier 1 emission factors by Tire 2 or 3 ones from process-based models. Future applying of the latter will allow accounting for CO2 source/sink strength of agricultural ecosystems, hence their complete GHG balance affected by soil, water, and climate.

Spectrally-resolved UV photodesorption of CH4 in pure and layered ices

NASA Astrophysics Data System (ADS)

Dupuy, R.; Bertin, M.; Féraud, G.; Michaut, X.; Jeseck, P.; Doronin, M.; Philippe, L.; Romanzin, C.; Fillion, J.-H.

2017-07-01

Context. Methane is among the main components of the ice mantles of interstellar dust grains, where it is at the start of a rich solid-phase chemical network. Quantification of the photon-induced desorption yield of these frozen molecules and understanding of the underlying processes is necessary to accurately model the observations and the chemical evolution of various regions of the interstellar medium. Aims: This study aims at experimentally determining absolute photodesorption yields for the CH4 molecule as a function of photon energy. The influence of the ice composition is also investigated. By studying the methane desorption from layered CH4:CO ice, indirect desorption processes triggered by the excitation of the CO molecules are monitored and quantified. Methods: Tunable monochromatic vacuum ultraviolet light (VUV) light from the DESIRS beamline of the SOLEIL synchrotron is used in the 7-13.6 eV (177-91 nm) range to irradiate pure CH4 or layers of CH4 deposited on top of CO ice samples. The release of species in the gas phase is monitored by quadrupole mass spectrometry, and absolute photodesorption yields of intact CH4 are deduced. Results: CH4 photodesorbs for photon energies higher than 9.1 eV ( 136 nm). The photodesorption spectrum follows the absorption spectrum of CH4, which confirms a desorption mechanism mediated by electronic transitions in the ice. When it is deposited on top of CO, CH4 desorbs between 8 and 9 eV with a pattern characteristic of CO absorption, indicating desorption induced by energy transfer from CO molecules. Conclusions: The photodesorption of CH4 from pure ice in various interstellar environments is around 2.0 ± 1.0 × 10-3 molecules per incident photon. Results on CO-induced indirect desorption of CH4 provide useful insights for the generalization of this process to other molecules co-existing with CO in ice mantles.

Effect of Thaw Depth on Fluxes of CO2 and CH4 in Manipulated Arctic Coastal Tundra of Barrow, Alaska

NASA Astrophysics Data System (ADS)

Kim, Y.

2014-12-01

Changes in CO2 and CH4 emissions represent one of the most significant consequences of drastic climate change in the Arctic, by way of thawing permafrost, a deepened active layer, and decline of thermokarst lakes in the Arctic. This study conducted flux-measurements of CO2 and CH4, as well as environmental factors such as temperature, moisture, and thaw depth, as part of a water table manipulation experiment in the Arctic coastal plain tundra of Barrow, Alaska during autumn. The manipulation treatment consisted of draining, controlling, and flooding treated sections by adjusting standing water. Inundation increased CH4 emission by a factor of 4.3 compared to non-flooded sections. This may be due to the decomposition of organic matter under a limited oxygen environment by saturated standing water. On the other hand, CO2 emission in the dry section was 3.9-fold higher than in others. CH4 emission tends to increase with deeper thaw depth, which strongly depends on the water table; however, CO2 emission is not related to thaw depth. Quotients of global warming potential (GWPCO2) (dry/control) and GWPCH4 (wet/control) increased by 464 and 148 %, respectively, and GWPCH4 (dry/control) declined by 66 %. This suggests that CO2 emission in a drained section is enhanced by soil and ecosystem respiration, and CH4 emission in a flooded area is likely stimulated under an anoxic environment by inundated standing water. The findings of this manipulation experiment during the autumn period demonstrate the different production processes of CO2 and CH4, as well as different global warming potentials, coupled with change in thaw depth. Thus the outcomes imply that the expansion of tundra lakes leads the enhancement of CH4 release, and the disappearance of the lakes causes the stimulated CO2 production in response to the Arctic climate change.

A new metal-organic framework for separation of C2H2/CH4 and CO2/CH4 at room temperature

NASA Astrophysics Data System (ADS)

Duan, Xing; Zhou, You; Lv, Ran; Yu, Ben; Chen, Haodong; Ji, Zhenguo; Cui, Yuanjing; Yang, Yu; Qian, Guodong

2018-04-01

A 3D microporous metal-organic framework with open Cu2+ sites and suitable pore space, [Cu2(L)(H2O)2]·(H2O)4(DMF)8 (ZJU-15, H4L = 5,5‧-(9H-carbazole-2,7-diyl)diisophthalic acid; DMF = N,N-dimethylformamide; ZJU = Zhejiang University), has been constructed and characterized. The activated ZJU-15a has three different types of cages and exhibits BET surface area of 1660 m2 g-1, and can separate gas mixture of C2H2/CH4 and CO2/CH4 at room temperature.

Additional Value of CH4 Measurement in a Combined 13C/H2 Lactose Malabsorption Breath Test: A Retrospective Analysis

PubMed Central

Houben, Els; De Preter, Vicky; Billen, Jaak; Van Ranst, Marc; Verbeke, Kristin

2015-01-01

The lactose hydrogen breath test is a commonly used, non-invasive method for the detection of lactose malabsorption and is based on an abnormal increase in breath hydrogen (H2) excretion after an oral dose of lactose. We use a combined 13C/H2 lactose breath test that measures breath 13CO2 as a measure of lactose digestion in addition to H2 and that has a better sensitivity and specificity than the standard test. The present retrospective study evaluated the results of 1051 13C/H2 lactose breath tests to assess the impact on the diagnostic accuracy of measuring breath CH4 in addition to H2 and 13CO2. Based on the 13C/H2 breath test, 314 patients were diagnosed with lactase deficiency, 138 with lactose malabsorption or small bowel bacterial overgrowth (SIBO), and 599 with normal lactose digestion. Additional measurement of CH4 further improved the accuracy of the test as 16% subjects with normal lactose digestion and no H2-excretion were found to excrete CH4. These subjects should have been classified as subjects with lactose malabsorption or SIBO. In conclusion, measuring CH4-concentrations has an added value to the 13C/H2 breath test to identify methanogenic subjects with lactose malabsorption or SIBO. PMID:26371034

Experimental ion mobility measurements in Xe-CH4

NASA Astrophysics Data System (ADS)

Perdigoto, J. M. C.; Cortez, A. F. V.; Veenhof, R.; Neves, P. N. B.; Santos, F. P.; Borges, F. I. G. M.; Conde, C. A. N.

2017-09-01

Data on ion mobility is important to improve the performance of large volume gaseous detectors. In the present work, the method, experimental setup and results for the ion mobility measurements in Xe-CH4 mixtures are presented. The results for this mixture show the presence of two distinct groups of ions. The nature of the ions depend on the mixture ratio since they are originated by both Xe and CH4. The results here presented were obtained for low reduced electric fields, E/N, 10-25 Td (2.4-6.1 kV ṡ cm-1 ṡ bar-1), at low pressure (8 Torr) (10.6 mbar), and at room temperature.

Joint CO2 and CH4 accountability for global warming.

PubMed

Smith, Kirk R; Desai, Manish A; Rogers, Jamesine V; Houghton, Richard A

2013-07-30

We propose a transparent climate debt index incorporating both methane (CH4) and carbon dioxide (CO2) emissions. We develop national historic emissions databases for both greenhouse gases to 2005, justifying 1950 as the starting point for global perspectives. We include CO2 emissions from fossil sources [CO2(f)], as well as, in a separate analysis, land use change and forestry. We calculate the CO2(f) and CH4 remaining in the atmosphere in 2005 from 205 countries using the Intergovernmental Panel on Climate Change's Fourth Assessment Report impulse response functions. We use these calculations to estimate the fraction of remaining global emissions due to each country, which is applied to total radiative forcing in 2005 to determine the combined climate debt from both greenhouse gases in units of milliwatts per square meter per country or microwatts per square meter per person, a metric we term international natural debt (IND). Australia becomes the most indebted large country per capita because of high CH4 emissions, overtaking the United States, which is highest for CO2(f). The differences between the INDs of developing and developed countries decline but remain large. We use IND to assess the relative reduction in IND from choosing between CO2(f) and CH4`control measures and to contrast the imposed versus experienced health impacts from climate change. Based on 2005 emissions, the same hypothetical impact on world 2050 IND could be achieved by decreasing CH4 emissions by 46% as stopping CO2 emissions entirely, but with substantial differences among countries, implying differential optimal strategies. Adding CH4 shifts the basic narrative about differential international accountability for climate change.

Evaluation of origins of CH4 carbon emitted from rice paddies

NASA Astrophysics Data System (ADS)

Watanabe, Akira; Takeda, Takuya; Kimura, Makoto

1999-10-01

Possible carbon sources for CH4 emitted from rice paddies are organic matter applied to the fields, such as rice straw (RS), soil organic matter (SOM), and carbon supplied from rice plants (RP), such as exudates and sloughed tissues. To estimate the contribution of each carbon source to CH4 emission, a pot experiment was conducted using 13C-enriched soil sample and 13C-enriched RS as tracers. The percentage contribution of RP carbon was estimated by subtraction. When RS was applied at a rate corresponding to 6 t ha-1, the percentage contributions of RS, SOM, and RP carbon to CH4 emission throughout the period of rice growth were 42%, 18-21%, and 37-40%, respectively. The values for SOM and RP carbon for the treatment in which RS was not applied were 15-20% and 80-85%, respectively. Seasonal variations in the percentage contribution of soil organic carbon to CH4 emission were small in the range between 13% and 30% for the pots with RS and between 15% and 24% for the pots without RS. In the RS-applied treatment, RS and SOM accounted for almost 100% of the CH4 carbon early in the period of rice growth, while 65-70% of the CH4 emission in the milky stage was derived from RP carbon.

A 4 U Laser Heterodyne Radiometer for Methane (CH4) and Carbon Dioxide (CO2) Measurements from an Occultation-Viewing CubSat

NASA Technical Reports Server (NTRS)

Wilson, Emily L.; DiGregorio, A. J.; Riot, Vincent J.; Ammons, Mark S.; Bruner, WIlliam W.; Carter, Darrell; Mao, Jianping; Ramanathan, Anand; Strahan, Susan E.; Oman, Luke D.;

A laser flash photolysis-resonance fluorescence kinetics study of the reaction Cl/2P/ + CH4 yields CH3 + HCl

NASA Technical Reports Server (NTRS)

Ravishankara, A. R.; Wine, P. H.

1980-01-01

The technique of laser flash photolysis-resonance fluorescence is employed to study the kinetics of the reaction Cl(2P) + CH4 yields CH3 + HCl over the temperature range 221-375 K. At temperatures less than or equal to 241 K the apparent bimolecular rate constant is found to be dependent upon the identity of the chemically inert gases in the reaction mixture. For Cl2/CH4/He reaction mixtures (total pressure = 50 torr) different bimolecular rate constants are measured at low and high methane concentrations. For Cl2/CH4/CCl/He and Cl2/CH4/Ar reaction mixtures, the bimolecular rate constant is independent of methane concentration, being approximately equal to the rate constant measured at low methane concentrations for Cl2/CH4/He mixtures. These rate constants are in good agreement with previous results obtained using the discharge flow-resonance fluorescence and competitive chlorination techniques. At 298 K the measured bimolecular rate constant is independent of the identity of the chemically inert gases in the reaction mixture and in good agreement with all previous investigations. The low-temperature results obtained in this investigation and all previous investigations can be rationalized in terms of a model which assumes that the Cl(2P 1/2) state reacts with CH4 much faster than the Cl(2P 3/2) state. Extrapolation of this model to higher temperatures, however, is not straightforward.

Transforming Growth Factor β1/Smad4 Signaling Affects Osteoclast Differentiation via Regulation of miR-155 Expression.

PubMed

Zhao, Hongying; Zhang, Jun; Shao, Haiyu; Liu, Jianwen; Jin, Mengran; Chen, Jinping; Huang, Yazeng

2017-03-01

Transforming growth factor β1 (TGFβ1)/Smad4 signaling plays a pivotal role in maintenance of the dynamic balance between bone formation and resorption. The microRNA miR-155 has been reported to exert a significant role in the differentiation of macrophage and dendritic cells. The goal of this study was to determine whether miR-155 regulates osteoclast differentiation through TGFβ1/Smad4 signaling. Here, we present that TGFβ1 elevated miR-155 levels during osteoclast differentiation through the stimulation of M-CSF and RANKL. Additionally, we found that silencing Smad4 attenuated the upregulation of miR-155 induced by TGFβ1. The results of luciferase reporter experiments and ChIP assays demonstrated that TGFβ1 promoted the binding of Smad4 to the miR-155 promoter at a site located in 454 bp from the transcription start site in vivo , further verifying that miR-155 is a transcriptional target of the TGFβ1/Smad4 pathway. Subsequently, TRAP staining and qRT-PCR analysis revealed that silencing Smad4 impaired the TGFβ1-mediated inhibition on osteoclast differentiation. Finally, we found that miR-155 may target SOCS1 and MITF to suppress osteoclast differentiation. Taken together, we provide the first evidence that TGFβ1/Smad4 signaling affects osteoclast differentiation by regulation of miR-155 expression and the use of miR-155 as a potential therapeutic target for osteoclast-related diseases shows great promise.

Dielectric Study of the Phase Transitions in [P(CH3)4]2CuY4 (Y = Cl, Br)

NASA Astrophysics Data System (ADS)

Gesi, Kazuo

2002-05-01

Phase transitions in [P(CH3)4]2CuY4 (Y = Cl, Br) have been studied by dielectric measurements. In [P(CH3)4]2CuCl4, a slight break and a discontinuous jump on the dielectric constant vs. temperature curve are seen at the normal-incommensurate and the incommensurate-commensurate phase transitions, respectively. A small peak of dielectric constant along the b-direction exists just above the incommensurate-to-commensurate transition temperature. The anisotropic dielectric anomalies of [P(CH3)4]2CuBr4 at phase transitions were measured along the three crystallographic axes. The pressure-temperature phase diagram of [P(CH3)4]2CuCl4 was determined. The initial pressure coefficients of the normal-to-incommensurate and the incommensurate-to-commensurate transition temperatures are 0.19 K/MPa and 0.27 K/MPa, respectively. The incommensurate phase in [P(CH3)4]2CuCl4 disappears at a triple point which exists at 335 MPa and 443 K. The stability and the pressure effects of the incommensurate phases are much different among the four [Z(CH3)4]2CuY4 crystals (Z = N, P; Y = Cl, Br).

The influence of meteorological variables on CO2 and CH4 trends recorded at a semi-natural station.

PubMed

Pérez, Isidro A; Sánchez, M Luisa; García, M Ángeles; Pardo, Nuria; Fernández-Duque, Beatriz

2018-03-01

CO 2 and CH 4 evolution is usually linked with sources, sinks and their changes. However, this study highlights the role of meteorological variables. It aims to quantify their contribution to the trend of these greenhouse gases and to determine which contribute most. Six years of measurements at a semi-natural site in northern Spain were considered. Three sections are established: the first focuses on monthly deciles, the second explores the relationship between pairs of meteorological variables, and the third investigates the relationship between meteorological variables and changes in CO 2 and CH 4 . In the first section, monthly outliers were more marked for CO 2 than for CH 4 . The evolution of monthly deciles was fitted to three simple expressions, linear, quadratic and exponential. The linear and exponential are similar, whereas the quadratic evolution is the most flexible since it provided a variable rate of concentration change and a better fit. With this last evolution, a decrease in the change rate was observed for low CO 2 deciles, whereas an increasing change rate prevailed for the rest and was more accentuated for CH 4 . In the second section, meteorological variables were provided by a trajectory model. Backward trajectories from 1-day prior to reaching the measurement site were used to calculate distance and direction averages as well as the recirculation factor. Terciles of these variables were determined in order to establish three intervals with low, medium and high values. These intervals were used to classify the variables following their interval widths and skewnesses. The best correlation between pairs of meteorological variables was observed for the average distance, in particular with horizontal wind speed. Sinusoidal relationships with the average direction were obtained for average distance and for vertical wind speed. Finally, in the third section, the quadratic evolution was considered in each interval of all the meteorological variables

Windrow composting mitigated CH4 emissions: characterization of methanogenic and methanotrophic communities in manure management.

PubMed

Chen, Ruirui; Wang, Yiming; Wei, Shiping; Wang, Wei; Lin, Xiangui

2014-12-01

With increasing livestock breeding, methane (CH4 ) emissions from manure management will increasingly contribute more to atmospheric CH4 concentration. The dynamics of methanogens and methanotrophs have not yet been studied in the manure environment. The current study combines surface CH4 emissions with methanogenic and methanotrophic community analyses from two management practices, windrow composting (WCOM) and solid storage (SSTO). Our results showed that there was an c. 50% reduction of CH4 emissions with WCOM compared with SSTO over a 50-day period. A sharp decrease in the quantities of both methanogens and methanotrophs in WCOM suggested that CH4 mitigation was mainly due to decreased CH4 production rather than increased CH4 oxidation. Pyrosequencing analysis demonstrated that aeration caused a clear shift of dominant methanogens in the manure, with specifically a significant decrease in Methanosarcina and increase in Methanobrevibacter. The composition of methanogenic community was influenced by manure management and regulated CH4 production. A sharp increase in the quantity of methanotrophs in SSTO suggested that microbial CH4 oxidation is an important sink for the CH4 produced. The increased abundance of Methylococcaceae in SSTO suggested that Type I methanotrophs have an advantage in CH4 oxidation in occupying niches under low CH4 and high O2 conditions. © 2014 Federation of European Microbiological Societies. Published by John Wiley & Sons Ltd. All rights reserved.

Harmonisation and diagnostics of MIPAS ESA CH4 and N2O profiles using data assimilation

NASA Astrophysics Data System (ADS)

Errera, Quentin; Ceccherini, Simone; Christophe, Yves; Chabrillat, Simon; Hegglin, Michaela I.; Lambert, Alyn; Ménard, Richard; Raspollini, Piera; Skachko, Sergey; van Weele, Michiel; Walker, Kaley A.

2016-12-01

This paper discusses assimilation experiments of methane (CH4) and nitrous oxide (N2O) profiles retrieved from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS). Here we focus on data versions 6 and 7 provided by the ESA processor. These data sets have been assimilated by the Belgian Assimilation System for Chemical ObsErvations (BASCOE). The CH4 and N2O retrieved profiles can oscillate, especially in the tropical lower stratosphere. Using the averaging kernels of the observations and a background error covariance matrix, which has previously been calibrated, allows the system to partly remedy this issue and provide assimilated fields that are more regular vertically. In general, there is a good agreement between the BASCOE analyses and independent observations from ACE-FTS (CH4 and N2O) and MLS (N2O), demonstrating the general good quality of CH4 and N2O retrievals provided by MIPAS ESA. Nevertheless, this study also identifies two issues in these data sets. First, time series of the observations show unexpected discontinuities due to an abrupt change in the gain of MIPAS band B, generally occurring after the instrument decontamination. Since the calibration is performed weekly, the abrupt change in the gain affects the measurements until the subsequent calibration is performed. Second, the correlations between BASCOE analyses and independent observations are poor in the lower stratosphere, especially in the tropics, probably due to the presence of outliers in the assimilated data. In this region, we recommend using MIPAS CH4 and N2O retrievals with caution.

Ozone perturbations by enhanced levels of CFCs, N2O, and CH4 A two-dimensional diabatic circulation study including uncertainty estimates

NASA Technical Reports Server (NTRS)

Isaksen, I. S. A.; Stordal, F.

1986-01-01

Observations made over the last few years suggest that the tropospheric concentrations of N2O, CH4, and O3 are increasing. Increases in the concentration of chlorofluorocarbons (CFCs) have been observed for some time. The present study is concerned with combined scenarios of future releases of N2O, CH4, and CFCs, which can affect the height profiles of ozone, while changes in latitudinal gradients of ozone may also be expected. Ozone perturbation calculations performed in the two-dimensional transport-chemistry model described by Stordal et al. (1985) are also presented, and the effects of increased levels of CFCs, N2O, and CH4 are examined. It is found that CH4 may be the most important ozone-perturbing trace species in connection with future tropospheric climatic impacts. A substantial increase in the tropospheric abundancy of CH4 could lead to large future ozone enhancements throughout the troposphere and lower stratosphere at middle and low latitudes.

CH4 emissions from European Major Population Centers: Results from aircraft-borne CH4 in-situ observations during EMeRGe-Europe campaign 2017

NASA Astrophysics Data System (ADS)

Roiger, A.; Klausner, T.; Schlager, H.; Ziereis, H.; Huntrieser, H.; Baumann, R.; Eirenschmalz, L.; Joeckel, P.; Mertens, M.; Fisher, R.; Bauguitte, S.; Young, S.; Andrés Hernández, M. D.

2017-12-01

Urban environments represent large and diffuse area sources of CH4 including emissions from pipeline leaks, industrial/sewage treatment plants, and landfills. However, there is little knowledge about the exact magnitude of these emissions and their contribution to total anthropogenic CH4. Especially in the context of an urbanizing world, a better understanding of the methane footprint of urban areas is crucial, both with respect to mitigation and projection of climate impacts. Aircraft-borne in-situ measurements are particularly useful to both quantify emissions from such area sources, as well as to study their impact on the regional distribution. However, airborne CH4 observations downstream of European cities are especially sparse.Here we report from aircraft-borne CH4 in-situ measurements as conducted during the HALO aircraft campaign EMeRGe (Effect of Megacities on the Transport and Transformation of Pollutants on the Regional to Global Scales) in July 2017, which was led by the University of Bremen, Germany. During seven research flights, emissions from a variety of European (Mega)-cities were probed at different altitudes from 3km down to 500m, including measurements in the outflows of London, Rome, Po Valley, Ruhr and Benelux. We will present and compare the CH4 distribution measured downstream of the various studied urban hot-spots. With the help of other trace gas measurements (including e.g. CO2, CO, O3, SO2), observed methane enhancements will be attributed to the different potential source types. Finally, by the combination of in-situ measurements and regional model simulations using the EMAC-MECO(n) model, the contribution of emissions from urban centers to the regional methane budget over Europe will be discussed.

Joint CO2 and CH4 accountability for global warming

PubMed Central

Smith, Kirk R.; Desai, Manish A.; Rogers, Jamesine V.; Houghton, Richard A.

2013-01-01

We propose a transparent climate debt index incorporating both methane (CH4) and carbon dioxide (CO2) emissions. We develop national historic emissions databases for both greenhouse gases to 2005, justifying 1950 as the starting point for global perspectives. We include CO2 emissions from fossil sources [CO2(f)], as well as, in a separate analysis, land use change and forestry. We calculate the CO2(f) and CH4 remaining in the atmosphere in 2005 from 205 countries using the Intergovernmental Panel on Climate Change’s Fourth Assessment Report impulse response functions. We use these calculations to estimate the fraction of remaining global emissions due to each country, which is applied to total radiative forcing in 2005 to determine the combined climate debt from both greenhouse gases in units of milliwatts per square meter per country or microwatts per square meter per person, a metric we term international natural debt (IND). Australia becomes the most indebted large country per capita because of high CH4 emissions, overtaking the United States, which is highest for CO2(f). The differences between the INDs of developing and developed countries decline but remain large. We use IND to assess the relative reduction in IND from choosing between CO2(f) and CH4`control measures and to contrast the imposed versus experienced health impacts from climate change. Based on 2005 emissions, the same hypothetical impact on world 2050 IND could be achieved by decreasing CH4 emissions by 46% as stopping CO2 emissions entirely, but with substantial differences among countries, implying differential optimal strategies. Adding CH4 shifts the basic narrative about differential international accountability for climate change. PMID:23847202

BOREAS TF-4 CO2 and CH4 Chamber Flux Data from the SSA

NASA Technical Reports Server (NTRS)

Anderson, Dean; Striegl, Robert; Wickland, Kimberly; Hall, Forrest G. (Editor); Conrad, Sara (Editor)

2000-01-01

The BOREAS TF-4 team measured fluxes of CO2 and CH4 across the soil-air interface in four ages of jack pine forest at the BOREAS SSA during August 1993 to March 1995. Gross and net flux of CO2 and flux of CH4 between soil and air are presented for 24 chamber sites in mature jack pine forest, 20-year-old, 4-year-old, and clear cut areas. The data are stored in tabular ASCII files.

Effects of the conversion of cropland to forest on the CH4 oxidation capacity in soils.

NASA Astrophysics Data System (ADS)

Bárcena, Teresa G.; D'Imperio, Ludovica; Priemé, Anders; Gundersen, Per; Vesterdal, Lars; Christiansen, Jesper R.

2013-04-01

As the second most important greenhouse gas (GHG) in the atmosphere, methane (CH4) plays a central role in global warming. Diverse types of soil have been reported as potential CH4 sinks due to the activity of methane oxidizing bacteria (MOB), underlining the importance of this functional group of microorganisms on a global basis. Agricultural practices are known to negatively affect CH4 oxidation in soil, while afforestation of former agricultural soils has been shown to enhance CH4 oxidation over time. However, knowledge is scarce with regard to the mechanisms driving the process of CH4 oxidation in different land uses. Our aim was to study the changes in CH4 uptake capacity in soils along a land-use change gradient from cropland to forest. We performed an incubation experiment to study the CH4 oxidation capacity of the top mineral soil (0-5 cm and 5-15 cm depth) for sites representing the transition from agriculture to afforestation based on monoculture of three tree species with different stand ages: pedunculate oak (4, 19, 42 and >200 years old), European larch (22 and 41 years old) and Norway spruce (15 and 43 years old). Main soil parameters were also measured to determine differences in soil properties between sites. Methane oxidation rates were related to the abundance of the soil methanotrophic community based on quantitative PCR (qPCR). In addition, we also estimated the abundance of ammonia-oxidizing bacteria (AOB) and archaea (AOA), in order to investigate the link between these two similar functional groups. Although present, the abundance of AOB was under detection limit. The effects and interactions among all measured variables were summarized by Principal Component Analysis (PCA). Along the gradient, CH4 oxidation increased with increasing stand age in both soil layers (ranging from 0-1.3 nmol g-1dw d-1). However, we detected significant differences, in particular between oak and spruce, suggesting a possible tree species effect on the CH4

Seasonality and interannual variability of CH4 fluxes from the eastern Amazon Basin inferred from atmospheric mole fraction profiles.

PubMed

Basso, Luana S; Gatti, Luciana V; Gloor, Manuel; Miller, John B; Domingues, Lucas G; Correia, Caio S C; Borges, Viviane F

2016-01-16

The Amazon Basin is an important region for global CH 4 emissions. It hosts the largest area of humid tropical forests, and around 20% of this area is seasonally flooded. In a warming climate it is possible that CH 4 emissions from the Amazon will increase both as a result of increased temperatures and precipitation. To examine if there are indications of first signs of such changes we present here a 13 year (2000-2013) record of regularly measured vertical CH 4 mole fraction profiles above the eastern Brazilian Amazon, sensitive to fluxes from the region upwind of Santarém (SAN), between SAN and the Atlantic coast. Using a simple mass balance approach, we find substantial CH 4 emissions with an annual average flux of 52.8 ± 6.8 mg CH 4 m -2  d -1 over an area of approximately 1 × 10 6  km 2 . Fluxes are highest in two periods of the year: in the beginning of the wet season and during the dry season. Using a CO:CH 4 emission factor estimated from the profile data, we estimated a contribution of biomass burning of around 15% to the total flux in the dry season, indicating that biogenic emissions dominate the CH 4 flux. This 13 year record shows that CH 4 emissions upwind of SAN varied over the years, with highest emissions in 2008 (around 25% higher than in 2007), mainly during the wet season, representing 19% of the observed global increase in this year.

Seasonality and interannual variability of CH4 fluxes from the eastern Amazon Basin inferred from atmospheric mole fraction profiles

PubMed Central

Gatti, Luciana V.; Gloor, Manuel; Miller, John B.; Domingues, Lucas G.; Correia, Caio S. C.; Borges, Viviane F.

2016-01-01

Abstract The Amazon Basin is an important region for global CH4 emissions. It hosts the largest area of humid tropical forests, and around 20% of this area is seasonally flooded. In a warming climate it is possible that CH4 emissions from the Amazon will increase both as a result of increased temperatures and precipitation. To examine if there are indications of first signs of such changes we present here a 13 year (2000–2013) record of regularly measured vertical CH4 mole fraction profiles above the eastern Brazilian Amazon, sensitive to fluxes from the region upwind of Santarém (SAN), between SAN and the Atlantic coast. Using a simple mass balance approach, we find substantial CH4 emissions with an annual average flux of 52.8 ± 6.8 mg CH4 m−2 d−1 over an area of approximately 1 × 106 km2. Fluxes are highest in two periods of the year: in the beginning of the wet season and during the dry season. Using a CO:CH4 emission factor estimated from the profile data, we estimated a contribution of biomass burning of around 15% to the total flux in the dry season, indicating that biogenic emissions dominate the CH4 flux. This 13 year record shows that CH4 emissions upwind of SAN varied over the years, with highest emissions in 2008 (around 25% higher than in 2007), mainly during the wet season, representing 19% of the observed global increase in this year. PMID:27642546

Observing and modeling links between soil moisture, microbes and CH4 fluxes from forest soils

NASA Astrophysics Data System (ADS)

Christiansen, Jesper; Levy-Booth, David; Barker, Jason; Prescott, Cindy; Grayston, Sue

2017-04-01

Soil moisture is a key driver of methane (CH4) fluxes in forest soils, both of the net uptake of atmospheric CH4 and emission from the soil. Climate and land use change will alter spatial patterns of soil moisture as well as temporal variability impacting the net CH4 exchange. The impact on the resultant net CH4 exchange however is linked to the underlying spatial and temporal distribution of the soil microbial communities involved in CH4 cycling as well as the response of the soil microbial community to environmental changes. Significant progress has been made to target specific CH4 consuming and producing soil organisms, which is invaluable in order to understand the microbial regulation of the CH4 cycle in forest soils. However, it is not clear as to which extent soil moisture shapes the structure, function and abundance of CH4 specific microorganisms and how this is linked to observed net CH4 exchange under contrasting soil moisture regimes. Here we report on the results from a research project aiming to understand how the CH4 net exchange is shaped by the interactive effects soil moisture and the spatial distribution CH4 consuming (methanotrophs) and producing (methanogens). We studied the growing season variations of in situ CH4 fluxes, microbial gene abundances of methanotrophs and methanogens, soil hydrology, and nutrient availability in three typical forest types across a soil moisture gradient in a temperate rainforest on the Canadian Pacific coast. Furthermore, we conducted laboratory experiments to determine whether the net CH4 exchange from hydrologically contrasting forest soils responded differently to changes in soil moisture. Lastly, we modelled the microbial mediation of net CH4 exchange along the soil moisture gradient using structural equation modeling. Our study shows that it is possible to link spatial patterns of in situ net exchange of CH4 to microbial abundance of CH4 consuming and producing organisms. We also show that the microbial

Molecular Level Investigation of CH 4 and CO 2 Adsorption in Hydrated Calcium–Montmorillonite

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Mal-Soon; McGrail, B. Peter; Rousseau, Roger

2017-11-17

We have studied the mechanism of intercalation and methane adsorption from a H2O/CH4/CO2 mixture on a prototypical shale component, Ca-montmorillonite. We employed ab initio molecular dynamics simulations at 323 K and 90 bar to obtain molecular level information of adsorption energetics, speciation, and structural and thermodynamic properties. Interaction of CH4 with surface Lewis acidic sites (Ca2+, surface OH) results in large induced dipoles (~1 D) that lead to relatively strong adsorption energies that level off once a full CH4 layer is formed. Intercalated CH4, also exhibits induced dipoles at low hydration levels, when the interaction with Ca2+ cations are lessmore » hindered. CO2 displaces CH4 in the coordination sphere of the cations (in the interlayer) or in the surface, thereby driving CH4 extraction. Our simulations indicate that there is a Goldilocks pressure range (~60-100 bar) where scCO2 –facilitated CH4 extraction will be maximized.« less

A 4 U laser heterodyne radiometer for methane (CH4) and carbon dioxide (CO2) measurements from an occultation-viewing CubeSat

NASA Astrophysics Data System (ADS)

Wilson, Emily L.; DiGregorio, A. J.; Riot, Vincent J.; Ammons, Mark S.; Bruner, William W.; Carter, Darrell; Mao, Jianping; Ramanathan, Anand; Strahan, Susan E.; Oman, Luke D.; Hoffman, Christine; Garner, Richard M.

2017-03-01

We present a design for a 4 U (20 cm  ×  20 cm  ×  10 cm) occultation-viewing laser heterodyne radiometer (LHR) that measures methane (CH4), carbon dioxide (CO2) and water vapor (H2O) in the limb that is designed for deployment on a 6 U CubeSat. The LHR design collects sunlight that has undergone absorption by the trace gas and mixes it with a distributive feedback (DFB) laser centered at 1640 nm that scans across CO2, CH4, and H2O absorption features. Upper troposphere/lower stratosphere measurements of these gases provide key inputs to stratospheric circulation models: measuring stratospheric circulation and its variability is essential for projecting how climate change will affect stratospheric ozone.

Space-Based Remote Imaging Spectroscopy of the Aliso Canyon CH4 Superemitter

NASA Technical Reports Server (NTRS)

Thompson, D. R.; Thorpe, A. K.; Frankenberg, C.; Green, R. O.; Duren, R.; Guanter, L.; Hollstein, A.; Middleton, E.; Ong, L.; Ungar, S.

2016-01-01

The Aliso Canyon gas storage facility near Porter Ranch, California, produced a large accidental CH4 release from October 2015 to February 2016. The Hyperion imaging spectrometer on board the EO-1 satellite successfully detected this event, achieving the first orbital attribution of CH4 to a single anthropogenic superemitter. Hyperion measured shortwave infrared signatures of CH4 near 2.3 microns at 0.01 micron spectral resolution and 30 meter spatial resolution. It detected the plume on three overpasses, mapping its magnitude and morphology. These orbital observations were consistent with measurements by airborne instruments. We evaluate Hyperion instrument performance, draw implications for future orbital instruments, and extrapolate the potential for a global survey of CH4 superemitters.

40 CFR Table C-2 to Subpart C of... - Default CH4 and N2O Emission Factors for Various Types of Fuel

Code of Federal Regulations, 2013 CFR

2013-07-01

... for Various Types of Fuel C Table C-2 to Subpart C of Part 98 Protection of Environment ENVIRONMENTAL... Fuel Combustion Sources Pt. 98, Subpt. C, Table C-2 Table C-2 to Subpart C of Part 98—Default CH4 and...) Default N2O emission factor (kg N2O/mmBtu) Coal and Coke (All fuel types in Table C-1) 1.1 × 10−02 1.6...

40 CFR Table C-2 to Subpart C of... - Default CH4 and N2O Emission Factors for Various Types of Fuel

Code of Federal Regulations, 2014 CFR

2014-07-01

... for Various Types of Fuel C Table C-2 to Subpart C of Part 98 Protection of Environment ENVIRONMENTAL... Fuel Combustion Sources Pt. 98, Subpt. C, Table C-2 Table C-2 to Subpart C of Part 98—Default CH4 and...) Default N2O emission factor (kg N2O/mmBtu) Coal and Coke (All fuel types in Table C-1) 1.1 × 10− 02 1.6...

Edaphic factors controlling summer (rainy season) greenhouse gas emissions (CO2 and CH4) from semiarid mangrove soils (NE-Brazil).

PubMed

Nóbrega, Gabriel N; Ferreira, Tiago O; Siqueira Neto, M; Queiroz, Hermano M; Artur, Adriana G; Mendonça, Eduardo De S; Silva, Ebenezer De O; Otero, Xosé L

2016-01-15

The soil attributes controlling the CO2, and CH4 emissions were assessed in semiarid mangrove soils (NE-Brazil) under different anthropogenic activities. Soil samples were collected from different mangroves under different anthropogenic impacts, e.g., shrimp farming (Jaguaribe River); urban wastes (Cocó River) and a control site (Timonha River). The sites were characterized according to the sand content; physicochemical parameters (Eh and pH); total organic C; soil C stock (SCS) and equivalent SCS (SCSEQV); total P and N; dissolved organic C (DOC); and the degree of pyritization (DOP). The CO2 and CH4 fluxes from the soils were assessed using static closed chambers. Higher DOC and SCS and the lowest DOP promote greater CO2 emission. The CH4 flux was only observed at Jaguaribe which presented higher DOP, compared to that found in mangroves from humid tropical climates. Semiarid mangrove soils cannot be characterized as important greenhouse gas sources, compared to humid tropical mangroves.

Regional Variation of CH4 and N2 Production Processes in the Deep Aquifers of an Accretionary Prism

PubMed Central

Matsushita, Makoto; Ishikawa, Shugo; Nagai, Kazushige; Hirata, Yuichiro; Ozawa, Kunio; Mitsunobu, Satoshi; Kimura, Hiroyuki

2016-01-01

Accretionary prisms are mainly composed of ancient marine sediment scraped from the subducting oceanic plate at a convergent plate boundary. Large amounts of anaerobic groundwater and natural gas, mainly methane (CH4) and nitrogen gas (N2), are present in the deep aquifers associated with an accretionary prism; however, the origins of these gases are poorly understood. We herein revealed regional variations in CH4 and N2 production processes in deep aquifers in the accretionary prism in Southwest Japan, known as the Shimanto Belt. Stable carbon isotopic and microbiological analyses suggested that CH4 is produced through the non-biological thermal decomposition of organic matter in the deep aquifers in the coastal area near the convergent plate boundary, whereas a syntrophic consortium of hydrogen (H2)-producing fermentative bacteria and H2-utilizing methanogens contributes to the significant production of CH4 observed in deep aquifers in midland and mountainous areas associated with the accretionary prism. Our results also demonstrated that N2 production through the anaerobic oxidation of organic matter by denitrifying bacteria is particularly prevalent in deep aquifers in mountainous areas in which groundwater is affected by rainfall. PMID:27592518

Regional Variation of CH4 and N2 Production Processes in the Deep Aquifers of an Accretionary Prism.

PubMed

Matsushita, Makoto; Ishikawa, Shugo; Nagai, Kazushige; Hirata, Yuichiro; Ozawa, Kunio; Mitsunobu, Satoshi; Kimura, Hiroyuki

2016-09-29

Accretionary prisms are mainly composed of ancient marine sediment scraped from the subducting oceanic plate at a convergent plate boundary. Large amounts of anaerobic groundwater and natural gas, mainly methane (CH4) and nitrogen gas (N2), are present in the deep aquifers associated with an accretionary prism; however, the origins of these gases are poorly understood. We herein revealed regional variations in CH4 and N2 production processes in deep aquifers in the accretionary prism in Southwest Japan, known as the Shimanto Belt. Stable carbon isotopic and microbiological analyses suggested that CH4 is produced through the non-biological thermal decomposition of organic matter in the deep aquifers in the coastal area near the convergent plate boundary, whereas a syntrophic consortium of hydrogen (H2)-producing fermentative bacteria and H2-utilizing methanogens contributes to the significant production of CH4 observed in deep aquifers in midland and mountainous areas associated with the accretionary prism. Our results also demonstrated that N2 production through the anaerobic oxidation of organic matter by denitrifying bacteria is particularly prevalent in deep aquifers in mountainous areas in which groundwater is affected by rainfall.

Airborne measurements of CO2, CH4 and HCN in boreal biomass burning plumes

NASA Astrophysics Data System (ADS)

O'Shea, Sebastian J.; Bauguitte, Stephane; Muller, Jennifer B. A.; Le Breton, Michael; Archibald, Alex; Gallagher, Martin W.; Allen, Grant; Percival, Carl J.

2013-04-01

Biomass burning plays an important role in the budgets of a variety of atmospheric trace gases and particles. For example, fires in boreal Russia have been linked with large growths in the global concentrations of trace gases such as CO2, CH4 and CO (Langenfelds et al., 2002; Simpson et al., 2006). High resolution airborne measurements of CO2, CH4 and HCN were made over Eastern Canada onboard the UK Atmospheric Research Aircraft FAAM BAe-146 from 12 July to 4 August 2011. These observations were made as part of the BORTAS project (Quantifying the impact of BOReal forest fires on Tropospheric oxidants over the Atlantic using Aircraft and Satellites). Flights were aimed at transecting and sampling the outflow from the commonly occurring North American boreal forest fires during the summer months and to investigate and identify the chemical composition and evolution of these plumes. CO2 and CH4 dry air mole fractions were determined using an adapted system based on a Fast Greenhouse Gas Analyser (FGGA, Model RMT-200) from Los Gatos Research Inc, which uses the cavity enhanced absorption spectroscopy technique. In-flight calibrations revealed a mean accuracy of 0.57 ppmv and 2.31 ppbv for 1 Hz observations of CO2 and CH4, respectively, during the BORTAS project. During these flights a number of fresh and photochemically-aged plumes were identified using simultaneous HCN measurements. HCN is a distinctive and useful marker for forest fire emissions and it was detected using chemical ionisation mass spectrometry (CIMS). In the freshest plumes, strong relationships were found between CH4, CO2 and other tracers for biomass burning. From this we were able to estimate that 8.5 ± 0.9 g of CH4 and 1512 ± 185 g of CO2 were released into the atmosphere per kg of dry matter burnt. These emission factors are in good agreement with estimates from previous studies and can be used to calculate budgets for the region. However for aged plumes the correlations between CH4 and other

Inverse modelling of European CH4 emissions during 2006-2012 using different inverse models and reassessed atmospheric observations

NASA Astrophysics Data System (ADS)

Bergamaschi, Peter; Karstens, Ute; Manning, Alistair J.; Saunois, Marielle; Tsuruta, Aki; Berchet, Antoine; Vermeulen, Alexander T.; Arnold, Tim; Janssens-Maenhout, Greet; Hammer, Samuel; Levin, Ingeborg; Schmidt, Martina; Ramonet, Michel; Lopez, Morgan; Lavric, Jost; Aalto, Tuula; Chen, Huilin; Feist, Dietrich G.; Gerbig, Christoph; Haszpra, László; Hermansen, Ove; Manca, Giovanni; Moncrieff, John; Meinhardt, Frank; Necki, Jaroslaw; Galkowski, Michal; O'Doherty, Simon; Paramonova, Nina; Scheeren, Hubertus A.; Steinbacher, Martin; Dlugokencky, Ed

2018-01-01

We present inverse modelling (top down) estimates of European methane (CH4) emissions for 2006-2012 based on a new quality-controlled and harmonised in situ data set from 18 European atmospheric monitoring stations. We applied an ensemble of seven inverse models and performed four inversion experiments, investigating the impact of different sets of stations and the use of a priori information on emissions. The inverse models infer total CH4 emissions of 26.8 (20.2-29.7) Tg CH4 yr-1 (mean, 10th and 90th percentiles from all inversions) for the EU-28 for 2006-2012 from the four inversion experiments. For comparison, total anthropogenic CH4 emissions reported to UNFCCC (bottom up, based on statistical data and emissions factors) amount to only 21.3 Tg CH4 yr-1 (2006) to 18.8 Tg CH4 yr-1 (2012). A potential explanation for the higher range of top-down estimates compared to bottom-up inventories could be the contribution from natural sources, such as peatlands, wetlands, and wet soils. Based on seven different wetland inventories from the Wetland and Wetland CH4 Inter-comparison of Models Project (WETCHIMP), total wetland emissions of 4.3 (2.3-8.2) Tg CH4 yr-1 from the EU-28 are estimated. The hypothesis of significant natural emissions is supported by the finding that several inverse models yield significant seasonal cycles of derived CH4 emissions with maxima in summer, while anthropogenic CH4 emissions are assumed to have much lower seasonal variability. Taking into account the wetland emissions from the WETCHIMP ensemble, the top-down estimates are broadly consistent with the sum of anthropogenic and natural bottom-up inventories. However, the contribution of natural sources and their regional distribution remain rather uncertain. Furthermore, we investigate potential biases in the inverse models by comparison with regular aircraft profiles at four European sites and with vertical profiles obtained during the Infrastructure for Measurement of the European Carbon

CO2, CH4, and DOC Flux During Long Term Thaw of High Arctic Tundra

NASA Astrophysics Data System (ADS)

Stackhouse, B. T.; Vishnivetskaya, T. A.; Layton, A.; Bennett, P.; Mykytczuk, N.; Lau, C. M.; Whyte, L.; Onstott, T. C.

2013-12-01

Arctic regions are expected to experience temperature increases of >4° C by the end of this century. This warming is projected to cause a drastic reduction in the extent of permafrost at high northern latitudes, affecting an estimated 1000 Pg of SOC in the top 3 m. Determining the effects of this temperature change on CO2 and CH4 emissions is critical for defining source constraints to global climate models. To investigate this problem, 18 cores of 1 m length were collected in late spring 2011 before the thawing of the seasonal active layer from an ice-wedge polygon near the McGill Arctic Research Station (MARS) on Axel Heiberg Island, Nunavut, Canada (N79°24, W90°45). Cores were collected from acidic soil (pH 5.5) with low SOC (~1%), summertime active layer depth between 40-70 cm (2010-2013), and sparse vegetation consisting primarily of small shrubs and sedges. Cores were progressively thawed from the surface over the course of 14 weeks to a final temperature of 4.5° C and held at that temperature for 15 months under the following conditions: in situ water saturation conditions versus fully water saturated conditions using artificial rain fall, surface light versus no surface light, cores from the polygon edge, and control cores with a permafrost table maintained at 70 cm depth. Core headspaces were measured weekly for CO2, CH4, H2, CO, and O2 flux during the 18 month thaw experiment. After ~20 weeks of thawing maximum, CO2 flux for the polygon edge and dark treatment cores were 3.0×0.7 and 1.7×0.4 mmol CO2 m-2 hr-1, respectively. The CO2 flux for the control, saturated, and in situ saturation cores reached maximums of 0.6×0.2, 0.9×0.5, and 0.9×0.1 mmol CO2 m-2 hr-1, respectively. Field measurements of CO2 flux from an adjacent polygon during the mid-summer of 2011 to 2013 ranged from 0.3 to 3.7 mmol CO2 m-2 hr-1. Cores from all treatments except water saturated were found to consistently oxidize CH4 at ~atmospheric concentrations (2 ppmv) with a maximum

Infrared absorption of 1-chloro-2-methyl-2-propyl [⋅C(CH3)2CH2Cl] and 2-chloro-2-methylpropyl [⋅CH2C(CH3)2Cl] radicals produced in the addition reactions of Cl with isobutene (i-C4H8) in solid para-hydrogen.

PubMed

Chou, Ching-Yin; Lee, Yuan-Pern

2016-10-07

The addition reactions of chlorine atom with isobutene (i-C 4 H 8 ) in solid para-hydrogen (p-H 2 ) were investigated with infrared (IR) absorption spectra. When a p-H 2 matrix containing Cl 2 and isobutene was irradiated with ultraviolet light at 365 nm, intense lines in a set at 534.5, 1001.0, 1212.9, 1366.0, 2961.6, and 2934.7 cm -1 , and several weaker others due to the 1-chloro-2-methyl-2-propyl radical, ⋅ C(CH 3 ) 2 CH 2 Cl, and those in a second set including intense ones at 642.7, 799.2, 1098.2, 1371.8, and 3027.3 cm -1 due to the 2-chloro-2-methylpropyl radical, ⋅ CH 2 C(CH 3 ) 2 Cl, appeared; the ratio of ⋅ C(CH 3 ) 2 CH 2 Cl to ⋅ CH 2 C(CH 3 ) 2 Cl was approximately (3 ± 1):1. The observed wavenumbers and relative intensities agree with the vibrational wavenumbers and IR intensities predicted with the B3PW91/aug-cc-pVTZ method. That the Cl atom adds to both carbons of the C=C bond of isobutene with the terminal site slightly favored is consistent with the energies of products predicted theoretically, but is in contrast to the reaction of Cl + propene in solid p-H 2 in which the addition of Cl to mainly the central C atom was previously reported. The role of the p-H 2 matrix in affecting the reaction paths is discussed. Absorption lines of the complex i-C 4 H 8 ⋅Cl 2 and the dichloro-product anti-1,2-dichloro-2-methylpropane, a-CH 2 ClCCl(CH 3 ) 2 , are also characterized.

High-pressure LOX/CH4 injector program

NASA Technical Reports Server (NTRS)

Wheeler, D. B.; Kirby, F. M.

1979-01-01

Two injector types, either coaxial or impinging elements, for high pressure LOX/CH4 operation with an existing 40K chamber are examined. A comparison is presented. The detailed fabrication drawings and supporting analysis are presented.

40 CFR Table Aa-1 to Subpart Aa of... - Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O AA Table AA-1 to Subpart AA of Part 98 Protection of Environment... Paper Manufacturing Pt. 98, Subpt. AA, Table AA-1 Table AA-1 to Subpart AA of Part 98—Kraft Pulping...

40 CFR Table Aa-1 to Subpart Aa of... - Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O AA Table AA-1 to Subpart AA of Part 98 Protection of Environment... Paper Manufacturing Pt. 98, Subpt. AA, Table AA-1 Table AA-1 to Subpart AA of Part 98—Kraft Pulping...

40 CFR Table Aa-1 to Subpart Aa of... - Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O AA Table AA-1 to Subpart AA of Part 98 Protection of Environment... Paper Manufacturing Pt. 98, Subpt. AA, Table AA-1 Table AA-1 to Subpart AA of Part 98—Kraft Pulping...

40 CFR Table Aa-1 to Subpart Aa of... - Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Kraft Pulping Liquor Emissions Factors for Biomass-Based CO2, CH4, and N2O AA Table AA-1 to Subpart AA of Part 98 Protection of Environment... Paper Manufacturing Pt. 98, Subpt. AA, Table AA-1 Table AA-1 to Subpart AA of Part 98—Kraft Pulping...

Integral and differential cross section measurements at low collision energies for the N2++CH4/CD4 reactions

NASA Astrophysics Data System (ADS)

Nicolas, Christophe; Torrents, Raquel; Gerlich, Dieter

2003-02-01

Absolute integral cross sections are measured in the collision energy range between 0.1 to 3.5 eV for the N2++CH4 and N2++CD4 reactions using the universal guided ion beam apparatus. The reaction branching ratio, CX3+:CX2+:N2X+ (X=H or D), is found to be 0.86:0.09:0.05 and 0.88:0.07:0.05 for the N2++CH4 and N2++CD4 reactions, respectively. The CH3+/CH2+ ratio is constant over the whole collision energy range and very similar to the one obtained for the almost isoenergetic Ar++CH4 reaction. Axial velocity distributions of the product ions are measured by time of flight at collision energies between 0.1 and 3.5 eV. The results provide direct insight into the reaction dynamics. The dissociative charge transfer channels, leading to CH3+ and CH2+ product ions, occur via an electron jump combined with some exchange of momentum between the colliding partners. The H (D) transfer leading to N2H+ can be described as a direct process, similar to a spectator stripping mechanism. Various isotope effects are observed, the dominant being that the cross sections for reaction with CH4 are up to 20% bigger than the corresponding ones for CD4.

Comparison of CH4 Emission from Rice Paddy Soils between Coastal Zone and Inland Regions

NASA Astrophysics Data System (ADS)

Sun, M.; Li, X.

2016-12-01

Numerous measurements of methane (CH4) emission fluxes have been carried out in rice paddy soil between coastal zone and inland regions. However, the differences of CH4 emission from rice paddy soils in these two locations were unavailable. A database of CH4 emission in paddy rice was compiled from previous published references and field observations with major parameters including water regimes, fertilizer application, CH4 fluxes, and environmental variables. Results showed that CH4 emission from inland paddy fields was significantly higher than that in the coastal zone (p < 0.05). Fertilizer application and water management played an important role in CH4 emission. The application of organic fertilizer and continuous flooding significantly promoted CH4 emission from paddy fields. CH4 fluxes showed significantly positive correlations with organic matter, total nitrogen, available potassium and annual temperature (R2 = 0.39, 0.53, 0.27 and 0.23, p < 0.05), and negative correlations with pH and available phosphorus (R2 = 0.29 and 0.37, p < 0.05). Significant differences occurred in available potassium between inland and coastal rice paddy (p < 0.05), which might account for the difference of CH4 emission between inland and coastal rice paddy. The contrasting of CH4 fluxes between inland and coastal wetlands could improve our understanding of the roles of rice paddies in the regional CH4 regulation. Our results also have implications for informing rice paddy management and climate change policy making the efforts being made by agricultural organizations and enterprises to restore coastal rice paddies for mitigating CH4 emissions.

Effects of prolonged soil drought on CH4 oxidation in a temperate spruce forest

NASA Astrophysics Data System (ADS)

Borken, W.; Brumme, R.; Xu, Y.-J.

2000-03-01

Our objective was to determine potential impacts of changes in rainfall amount and distribution on soil CH4 oxidation in a temperate forest ecosystem. We constructed a roof below the canopy of a 65-year-old Norway spruce forest (Picea abies (L.) Karst.) and simulated two climate change scenarios: (1) an extensively prolonged summer drought of 172 days followed by a rewetting period of 19 days in 1993 and (2) a less intensive summer drought of 108 days followed by a rewetting period of 33 days in 1994. CH4 oxidation, soil matric potential, and soil temperature were measured hourly to daily over a 2-year period. The results showed that annual CH4 oxidation in the drought experiment increased by 102% for the climate change scenario 1 and by 41% for the climate change scenario 2, compared to those of the ambient plot (1.33 kg CH4 ha-1 in 1993 and 1.65 kg CH4 ha-1 in 1994). We tested the relationships between CH4 oxidation rates, water-filled pore space (WFPS), soil matric potential, gas diffusivity, and soil temperature. Temporal variability in the CH4 oxidation rates corresponded most closely to soil matric potential. Employing soil matric potential and soil temperature, we developed a nonlinear model for estimating CH4 oxidation rates. Modeled results were in strong agreement with the measured CH4 oxidation for the ambient (r2 = 0.80) and drought plots (r2 = 0.89) over two experimental years, suggesting that soil matric potential is a highly reliable parameter for modeling CH4 oxidation rate.

Transforming Growth Factor β1/Smad4 Signaling Affects Osteoclast Differentiation via Regulation of miR-155 Expression

PubMed Central

Zhao, Hongying; Zhang, Jun; Shao, Haiyu; Liu, Jianwen; Jin, Mengran; Chen, Jinping; Huang, Yazeng

2017-01-01

Transforming growth factor β1 (TGFβ1)/Smad4 signaling plays a pivotal role in maintenance of the dynamic balance between bone formation and resorption. The microRNA miR-155 has been reported to exert a significant role in the differentiation of macrophage and dendritic cells. The goal of this study was to determine whether miR-155 regulates osteoclast differentiation through TGFβ1/Smad4 signaling. Here, we present that TGFβ1 elevated miR-155 levels during osteoclast differentiation through the stimulation of M-CSF and RANKL. Additionally, we found that silencing Smad4 attenuated the upregulation of miR-155 induced by TGFβ1. The results of luciferase reporter experiments and ChIP assays demonstrated that TGFβ1 promoted the binding of Smad4 to the miR-155 promoter at a site located in 454 bp from the transcription start site in vivo, further verifying that miR-155 is a transcriptional target of the TGFβ1/Smad4 pathway. Subsequently, TRAP staining and qRT-PCR analysis revealed that silencing Smad4 impaired the TGFβ1-mediated inhibition on osteoclast differentiation. Finally, we found that miR-155 may target SOCS1 and MITF to suppress osteoclast differentiation. Taken together, we provide the first evidence that TGFβ1/Smad4 signaling affects osteoclast differentiation by regulation of miR-155 expression and the use of miR-155 as a potential therapeutic target for osteoclast-related diseases shows great promise. PMID:28359146

Is CH4 consumption by soils controlled by physics or biology? Results from a study of plot-scale variability of greenhouse gas fluxes

NASA Astrophysics Data System (ADS)

Maier, Martin; Paulus, Sinikka; Nicolai, Clara; Nauer, Philipp

2017-04-01

Soil-atmosphere fluxes of trace gases vary on different spatial scales, between landscapes and ecosystems down to the plot scale within apparently homogenous sites. The production and consumption of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) underlie different spatial and temporal changes, und thus, their interrelation is difficult to unravel. Small-scale variability in soil properties is well-known from soil surveys, affecting theoretically water availability for plants, soil aeration, vegetation, the local photosynthesis rate, and, eventually, greenhouse gas fluxes. We investigated the small scale variability of greenhouse gas fluxes in a homogenous Scots Pine stand in a former riparian flood plain. Soil-atmosphere fluxes of carbon dioxide (CO2), methane (CH4) and nitrous oxide (N2O) were carried out at 60 points on a 250 m2 plot with strata of diverse soil substrates and understory vegetation. Gas flux measurements were combined with soil physical lab measurements, and a soil vegetation survey. The soil was a source of CO2 and a sink for CH4 and N2O. No correlations between the fluxes and only weak correlations between the fluxes and soil physical factors were observed. CH4 and CO2 fluxes were significantly different for the soil-vegetation strata. Separating the dataset into the different soil-vegetation strata showed that CH4 consumption increased significantly with soil gas diffusivity and soil respiration. Methane consumption in the silt stratum was higher at a given soil gas diffusivity than in the sand stratum, indicating a higher methanotrophic microbe population and thus better habitats in silt. CH4 consumption increased with soil respiration in all strata, so that we speculate that the rhizosphere and decomposing organic litter (as origin of most of the soil respiration) facilitate a preferred habitat of methanotrophic microbes. The patterns of N2O consumption were more complex, but consumption seemed to be limited at locations with

Synergistic effects of plasma-catalyst interactions for CH4 activation.

PubMed

Kim, Jongsik; Go, David B; Hicks, Jason C

2017-05-24

The elucidation of catalyst surface-plasma interactions is a challenging endeavor and therefore requires thorough and rigorous assessment of the reaction dynamics on the catalyst in the plasma environment. The first step in quantifying and defining catalyst-plasma interactions is a detailed kinetic study that can be used to verify appropriate reaction conditions for comparison and to discover any unexpected behavior of plasma-assisted reactions that might prevent direct comparison. In this paper, we provide a kinetic evaluation of CH 4 activation in a dielectric barrier discharge plasma in order to quantify plasma-catalyst interactions via kinetic parameters. The dry reforming of CH 4 with CO 2 was studied as a model reaction using Ni supported on γ-Al 2 O 3 at temperatures of 790-890 K under atmospheric pressure, where the partial pressures of CH 4 (or CO 2 ) were varied over a range of ≤25.3 kPa. Reaction performance was monitored by varying gas hourly space velocity, plasma power, bulk gas temperature, and reactant concentration. After correcting for gas-phase plasma reactions, a linear relationship was observed in the log of the measured rate constant with respect to reciprocal power (1/power). Although thermal catalysis displays typical Arrhenius behavior for this reaction, plasma-assisted catalysis occurs from a complex mixture of sources and shows non-Arrhenius behavior. However, an energy barrier was obtained from the relationship between the reaction rate constant and input power to exhibit ≤∼20 kJ mol -1 (compared to ∼70 kJ mol -1 for thermal catalysis). Of additional importance, the energy barriers measured during plasma-assisted catalysis were relatively consistent with respect to variations in total flow rates, types of diluent, or bulk reaction temperature. These experimental results suggest that plasma-generated vibrationally-excited CH 4 favorably interacts with Ni sites at elevated temperatures, which helps reduce the energy barrier

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

NASA Astrophysics Data System (ADS)

Loring, J.; Thompson, C.; Ilton, E. S.; McGrail, B. P.; Schaef, T.

2014-12-01

Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2 -enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of a Na-saturated montmorillonite (Na-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane and mixtures of methane and carbon dioxide were investigated usingCH4 IR spectroscopic titrations andCH4 XRD. The goals were to (1) determine if the hydration/expansion behavior of the clay in supercritical methane is different than in supercritical CO2, (2) determine if methane intercalates the clay, and (3) probe the effects of increasing CO2 concentrations. IR spectra were collected as Na-SWy-2 was titrated with water under several fluid exposures: pure methane, 25, 50, and 75 mole% CO2 in methane, and pure CO2. ComplementaryCH4 XRD experiments were conducted in the same fluids at discrete dissolved water concentrations to measure the d001 values of the clay and thus its volume change on hydration and CH4 and/or CO2 intercalation. In pure methane, no direct evidence of CH4 intercalation was detected in CH bending or stretching regions of the IR spectra. Similarly, in situ XRD indicated the montmorillonite structure was stable in the presence of CH4 and no measurable changes to the basal spacing were observed. However, under low water conditions where the montmorillonite structure was partially expanded (~sub 1W), the IR data indicated a rapid intercalation of CO2 into the interlayer, even with fluid mixtures containing the

Disproportionation and thermochemical sulfate reduction reactions in S-H20-Ch4 and S-D2O-CH4 systems from 200 to 340 °C at elevated pressures

USGS Publications Warehouse

Yuan, Shunda; Chou, I-Ming; Burruss, Robert A.

2013-01-01

Elemental sulfur, as a transient intermediate compound, by-product, or catalyst, plays significant roles in thermochemical sulfate reduction (TSR) reactions. However, the mechanisms of the reactions in S-H2O-hydrocarbons systems are not clear. To improve our understanding of reaction mechanisms, we conducted a series of experiments between 200 and 340 °C for S-H2O-CH4, S-D2O-CH4, and S-CH4-1m ZnBr2 systems in fused silica capillary capsules (FSCC). After a heating period ranging from 24 to 2160 hours (hrs), the quenched samples were analyzed by Raman spectroscopy. Combined with the in situ Raman spectra collected at high temperatures and pressures in the S-H2O and S-H2O-CH4 systems, our results showed that (1) the disproportionation of sulfur in the S-H2O-CH4 system occurred at temperatures above 200 °C and produced H2S, SO42-, and possibly trace amount of HSO4-; (2) sulfate (and bisulfate), in the presence of sulfur, can be reduced by methane between 250 and 340 °C to produce CO2 and H2S, and these TSR temperatures are much closer to those of the natural system (2O-CH4 system may take place simultaneously, with TSR being favored at higher temperatures; and (4) in the system S-D2O-CH4, both TSR and the competitive disproportionation reactions occurred simultaneously at temperatures above 300 °C, but these reactions were very slow at lower temperatures. Our observation of methane reaction at 250 °C in a laboratory time scale suggests that, in a geologic time scale, methane may be destroyed by TSR reactions at temperatures > 200 °C that can be reached by deep drilling for hydrocarbon resources.

Isotopomer analysis of production and consumption mechanisms of N2O and CH4 in an advanced wastewater treatment system.

PubMed

Toyoda, Sakae; Suzuki, Yuuri; Hattori, Shohei; Yamada, Keita; Fujii, Ayako; Yoshida, Naohiro; Kouno, Rina; Murayama, Kouki; Shiomi, Hiroshi

2011-02-01

Wastewater treatment processes are believed to be anthropogenic sources of nitrous oxide (N(2)O) and methane (CH(4)). However, few studies have examined the mechanisms and controlling factors in production of these greenhouse gases in complex bacterial systems. To elucidate production and consumption mechanisms of N(2)O and CH(4) in microbial consortia during wastewater treatment and to characterize human waste sources, we measured their concentrations and isotopomer ratios (elemental isotope ratios and site-specific N isotope ratios in asymmetric molecules of NNO) in water and gas samples collected by an advanced treatment system in Tokyo. Although the estimated emissions of N(2)O and CH(4) from the system were found to be lower than those from the typical treatment systems reported before, water in biological reaction tanks was supersaturated with both gases. The concentration of N(2)O, produced mainly by nitrifier-denitrification as indicated by isotopomer ratios, was highest in the oxic tank (ca. 4000% saturation). The dissolved CH(4) concentration was highest in in-flow water (ca. 3000% saturation). It decreased gradually during treatment. Its carbon isotope ratio indicated that the decrease resulted from bacterial CH(4) oxidation and that microbial CH(4) production can occur in anaerobic and settling tanks.

Infrared spectroscopy of solid normal hydrogen doped with CH3F and O2 at 4.2 K: CH3F:O2 complex and CH3F migration

NASA Astrophysics Data System (ADS)

Abouaf-Marguin, L.; Vasserot, A.-M.

2011-04-01

Double doping of solid normal hydrogen with CH3F and O2 at about 4.2 K gives evidence of (ortho-H2)n:CH3F clusters and of O2:CH3F complex formation. FTIR analysis of the time evolution of the spectra in the region of the v3 C-F stretching mode indicates that these clusters behave very differently from (ortho-H2)n:H2O clusters. The main point is the observed migration of CH3F molecules in solid para-H2 at 4.2 K which differs from that of H2O under identical experimental conditions. This is confirmed by an increase over time of the integrated intensity of the CH3F:O2 complex with a rate constant K = 2.7(2) . 10-4 s-1.

Measurements and modeling of long-path 12CH4 spectra in the 4800-5300 cm-1 region

NASA Astrophysics Data System (ADS)

Nikitin, A. V.; Thomas, X.; Régalia, L.; Daumont, L.; Rey, M.; Tashkun, S. A.; Tyuterev, Vl. G.; Brown, L. R.

2014-05-01

A new study of 12CH4 line positions and intensities was performed for the lower portion of the Tetradecad region between 4800 and 5300 cm-1 using long path (1603 m) spectra of normal sample CH4 at three pressures recorded with the Fourier transform spectrometer in Reims, France. Line positions and intensities were retrieved by least square curve-fitting procedures and analyzed using the effective Hamiltonian and the effective Dipole moment expressed in terms of irreducible tensor operators adapted to spherical top molecules. An existing spectrum of enriched 13CH4 was used to discern the isotopic lines. A new measured linelist produced positions and intensities for 5851 features (a factor of two more than prior work). Assignments were made for 46% of these; 2725 experimental line positions and 1764 selected line intensities were fitted with RMS standard deviations of 0.004 cm-1 and 7.3%, respectively. The RMS of prior intensity fits of the lower Tetradecad was previously a factor of two worse. The sum of observed intensities between 4800 and 5300 cm-1 fell within 5% of the predicted value from variational calculations.

Local- and regional-scale measurements of CH4, δ13CH4, and C2H6 in the Uintah Basin using a mobile stable isotope analyzer

NASA Astrophysics Data System (ADS)

Rella, C. W.; Hoffnagle, J.; He, Y.; Tajima, S.

2015-10-01

In this paper, we present an innovative CH4, δ13CH4, and C2H6 instrument based on cavity ring-down spectroscopy (CRDS). The design and performance of the analyzer is presented in detail. The instrument is capable of precision of less than 1 ‰ on δ13CH4 with 1 in. of averaging and about 0.1 ‰ in an hour. Using this instrument, we present a comprehensive approach to atmospheric methane emissions attribution. Field measurements were performed in the Uintah Basin (Utah, USA) in the winter of 2013, using a mobile lab equipped with the CRDS analyzer, a high-accuracy GPS, a sonic anemometer, and an onboard gas storage and playback system. With a small population and almost no other sources of methane and ethane other than oil and gas extraction activities, the Uintah Basin represents an ideal location to investigate and validate new measurement methods of atmospheric methane and ethane. We present the results of measurements of the individual fugitive emissions from 23 natural gas wells and six oil wells in the region. The δ13CH4 and C2H6 signatures that we observe are consistent with the signatures of the gases found in the wells. Furthermore, regional measurements of the atmospheric CH4, δ13CH4, and C2H6 signatures throughout the basin have been made, using continuous sampling into a 450 m long tube and laboratory reanalysis with the CRDS instrument. These measurements suggest that 85 ± 7 % of the total emissions in the basin are from natural gas production.

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br

NASA Technical Reports Server (NTRS)

Hsu, K.-J.; Demore, W. B.

1994-01-01

Rate constants for the reactions of OH with CH3Cl, CH2Cl2, CHCl3, and CH3Br have been measured by a relative rate technique in which the reaction rate of each compound was compared to that of HFC-152a (CH3CHF2) and (for CH2Cl2) HFC-161 (CH3CH2F). Using absolute rate constants for HFC-152a and HFC-161, which we have determined relative to those for CH4, CH3CCl3, and C2H6, temperature dependent rate constants of both compounds were derived. The derived rate constant for CH3Br is in good agreement with recent absolute measurements. However, for the chloromethanes all the rate constants are lower at atmospheric temperatures than previously reported, especially for CH2Cl2 where the present rate constant is about a factor of 1.6 below the JPL 92-20 value. The new rate constant appears to resolve a discrepancy between the observed atmospheric concentrations and those calculated from the previous rate constant and estimated release rates.

CH4 and N2O emissions from China's beef feedlots with ad libitum and restricted feeding in fall and spring seasons.

PubMed

Lin, Zhi; Liao, Wenhua; Yang, Yuanyuan; Gao, Zhiling; Ma, Wenqi; Wang, Dianwu; Cao, Yufeng; Li, Jianguo; Cai, Zhenjiang

2015-04-01

Accurately quantifying methane (CH4) and nitrous oxide (N2O) emissions from beef operations in China is necessary to evaluate the contribution of beef cattle to greenhouse gas budgets at the national and global level. Methane and N2O emissions from two intensive beef feedlots in the North China Plain, one with a restricted feeding strategy and high manure collection frequency and the other with an ad libitum feeding strategy and low manure collection frequency, were quantified in the fall and spring seasons using an inverse dispersion technique. The diel pattern of CH4 from the beef feedlot with an ad libitum feed strategy (single peak during a day) differed from that under a restricted feeding condition (multiple peaks during a day), but little difference in the diel pattern of N2O emissions between two feeding strategies was observed. The two-season average CH4 emission rates of the two intensive feedlots were 230 and 198gCH4animal(-1)d(-1) and accounted for 6.7% and 6.8% of the gross energy intake, respectively, indicating little impact of the feeding strategy and manure collection frequency on the CH4 conversion factor at the feedlot level. However, the average N2O emission rates (21.2g N2Oanimal(-1)d(-1)) and conversion factor (8.5%) of the feedlot with low manure collection frequency were approximately 131% and 174% greater, respectively, than the feedlot under high frequency conditions, which had a N2O emission rate and conversion factor of 9.2g N2Oanimal(-1)d(-1) and 3.1%, respectively, indicating that increasing manure collection frequency played an important role in reducing N2O emissions from beef feedlots. In addition, comparison indicated that China's beef and dairy cattle in feedlots appeared to have similar CH4 conversion factors. Copyright © 2015 Elsevier Inc. All rights reserved.

Fluxes of N2O and CH4 from forest and grassland lysimeter soils in response to simulated climate change

NASA Astrophysics Data System (ADS)

Weymann, Daniel; Brueggemann, Nicolas; Puetz, Thomas; Vereecken, Harry

2015-04-01

Central Europe is expected to be exposed to altered temperature and hydrological conditions, which will affect the vulnerability of nitrogen and carbon cycling in soils and thus production and fluxes of climate relevant trace gases. However, knowledge of the response of greenhouse gas fluxes to climate change is limited so far, but will be an important basis for future climate projections. Here we present preliminary results of an ongoing lysimeter field study which aims to assess the impact of simulated climate change on N2O and CH4 fluxes from a forest and a fertilized grassland soil. The lysimeters are part of the Germany-wide research infrastructure TERENO, which investigates feedbacks of climate change to the pedosphere on a long-term scale. Lysimeters (A = 1m2) were established in 2010 at high elevated sites (HE, 500 and 600 m.a.s.l.) and subsequently transferred along an altitudinal gradient to a low elevated site (LE, 100 m.a.s.l.) within the Eifel / Lower Rhine Valley Observatory in Western Germany, thereby resulting in a temperature increase of 2.3 K whereas precipitation decreased by 160 mm during the present study period. Systematic monitoring of soil-atmosphere exchange of N2O and CH4 based on weekly manual closed chamber measurements at HE and LE sites has started in August 2013. Furthermore, we routinely determine dissolved N2O and CH4 concentrations in the seepage water using a headspace equilibration technique and record water discharge in order to quantify leaching losses of both greenhouse gases. Cumulative N2O fluxes clearly responded to simulated climate change conditions and increased by 250 % and 600 % for the forest and the grassland soil, respectively. This difference between the HE and LE sites was mainly caused by an exceptionally heavy precipitation event in July 2014 which turned the LE site sustainably to a consistently higher emission level. Nonetheless, emissions remained rather small and ranged between 20 and 40 μg m-2 h-1. In

Simulated nitrogen deposition reduces CH4 uptake and increases N2O emission from a subtropical plantation forest soil in southern China.

PubMed

Wang, Yongsheng; Cheng, Shulan; Fang, Huajun; Yu, Guirui; Xu, Minjie; Dang, Xusheng; Li, Linsen; Wang, Lei

2014-01-01

To date, few studies are conducted to quantify the effects of reduced ammonium (NH4+) and oxidized nitrate (NO3-) on soil CH4 uptake and N2O emission in the subtropical forests. In this study, NH4Cl and NaNO3 fertilizers were applied at three rates: 0, 40 and 120 kg N ha(-1) yr(-1). Soil CH4 and N2O fluxes were determined twice a week using the static chamber technique and gas chromatography. Soil temperature and moisture were simultaneously measured. Soil dissolved N concentration in 0-20 cm depth was measured weekly to examine the regulation to soil CH4 and N2O fluxes. Our results showed that one year of N addition did not affect soil temperature, soil moisture, soil total dissolved N (TDN) and NH4+-N concentrations, but high levels of applied NH4Cl and NaNO3 fertilizers significantly increased soil NO3(-)-N concentration by 124% and 157%, respectively. Nitrogen addition tended to inhibit soil CH4 uptake, but significantly promoted soil N2O emission by 403% to 762%. Furthermore, NH4+-N fertilizer application had a stronger inhibition to soil CH4 uptake and a stronger promotion to soil N2O emission than NO3(-)-N application. Also, both soil CH4 and N2O fluxes were driven by soil temperature and moisture, but soil inorganic N availability was a key integrator of soil CH4 uptake and N2O emission. These results suggest that the subtropical plantation soil sensitively responses to atmospheric N deposition, and inorganic N rather than organic N is the regulator to soil CH4 uptake and N2O emission.

A direct numerical simulation study of flame structure and stabilization of an experimental high Ka CH 4/air premixed jet flame

DOE PAGES

Wang, Haiou; Hawkes, Evatt R.; Chen, Jacqueline H.

2017-03-17

In the present work, a direct numerical simulation (DNS) of an experimental high Karlovitz number (Ka) CH 4/air piloted premixed flame was analyzed to study the inner structure and the stabilization mechanism of the turbulent flame. A reduced chemical mechanism for premixed CH 4/air combustion with NO x based on GRI-Mech3.0 was used, including 268 elementary reactions and 28 transported species. The evolution of the stretch factor, I0, indicates that the burning rate per unit flame surface area is considerably reduced in the near field and exhibits a minimum at x/D = 8. Downstream, the burning rate gradually increases. Themore » stretch factor is different between different species, suggesting the quenching of some reactions but not others. Comparison between the turbulent flame and strained laminar flames indicates that certain aspects of the mean flame structure can be represented surprisingly well by flamelets if changes in boundary conditions are accounted for and the strain rate of the mean flow is employed; however, the thickening of the flame due to turbulence is not captured. The spatial development of displacement speeds is studied at higher Ka than previous DNS. In contrast to almost all previous studies, the mean displacement speed conditioned on the flame front is negative in the near field, and the dominant contribution to the displacement speed is normal diffusion with the reaction contribution being secondary. Further downstream, reaction overtakes normal diffusion, contributing to a positive displacement speed. The negative displacement speed in the near field implies that the flame front situates itself in the pilot region where the inner structure of the turbulent flame is affected significantly, and the flame stabilizes in balance with the inward flow. Notably, in the upstream region of the turbulent flame, the main reaction contributing to the production of OH, H+O 2⇌O+OH (R35), is weak. Moreover, oxidation reactions, H 2+OH⇌H+H 2O (R79

A direct numerical simulation study of flame structure and stabilization of an experimental high Ka CH 4/air premixed jet flame

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Haiou; Hawkes, Evatt R.; Chen, Jacqueline H.

In the present work, a direct numerical simulation (DNS) of an experimental high Karlovitz number (Ka) CH 4/air piloted premixed flame was analyzed to study the inner structure and the stabilization mechanism of the turbulent flame. A reduced chemical mechanism for premixed CH 4/air combustion with NO x based on GRI-Mech3.0 was used, including 268 elementary reactions and 28 transported species. The evolution of the stretch factor, I0, indicates that the burning rate per unit flame surface area is considerably reduced in the near field and exhibits a minimum at x/D = 8. Downstream, the burning rate gradually increases. Themore » stretch factor is different between different species, suggesting the quenching of some reactions but not others. Comparison between the turbulent flame and strained laminar flames indicates that certain aspects of the mean flame structure can be represented surprisingly well by flamelets if changes in boundary conditions are accounted for and the strain rate of the mean flow is employed; however, the thickening of the flame due to turbulence is not captured. The spatial development of displacement speeds is studied at higher Ka than previous DNS. In contrast to almost all previous studies, the mean displacement speed conditioned on the flame front is negative in the near field, and the dominant contribution to the displacement speed is normal diffusion with the reaction contribution being secondary. Further downstream, reaction overtakes normal diffusion, contributing to a positive displacement speed. The negative displacement speed in the near field implies that the flame front situates itself in the pilot region where the inner structure of the turbulent flame is affected significantly, and the flame stabilizes in balance with the inward flow. Notably, in the upstream region of the turbulent flame, the main reaction contributing to the production of OH, H+O 2⇌O+OH (R35), is weak. Moreover, oxidation reactions, H 2+OH⇌H+H 2O (R79

Global Analysis of Transcription Factor-Binding Sites in Yeast Using ChIP-Seq

PubMed Central

Lefrançois, Philippe; Gallagher, Jennifer E. G.; Snyder, Michael

2016-01-01

Transcription factors influence gene expression through their ability to bind DNA at specific regulatory elements. Specific DNA-protein interactions can be isolated through the chromatin immunoprecipitation (ChIP) procedure, in which DNA fragments bound by the protein of interest are recovered. ChIP is followed by high-throughput DNA sequencing (Seq) to determine the genomic provenance of ChIP DNA fragments and their relative abundance in the sample. This chapter describes a ChIP-Seq strategy adapted for budding yeast to enable the genome-wide characterization of binding sites of transcription factors (TFs) and other DNA-binding proteins in an efficient and cost-effective way. Yeast strains with epitope-tagged TFs are most commonly used for ChIP-Seq, along with their matching untagged control strains. The initial step of ChIP involves the cross-linking of DNA and proteins. Next, yeast cells are lysed and sonicated to shear chromatin into smaller fragments. An antibody against an epitope-tagged TF is used to pull down chromatin complexes containing DNA and the TF of interest. DNA is then purified and proteins degraded. Specific barcoded adapters for multiplex DNA sequencing are ligated to ChIP DNA. Short DNA sequence reads (28–36 base pairs) are parsed according to the barcode and aligned against the yeast reference genome, thus generating a nucleotide-resolution map of transcription factor-binding sites and their occupancy. PMID:25213249

Influence of Structural Heterogeneity on Diffusion of CH4 and CO2 in Silicon Carbide-Derived Nanoporous Carbon

PubMed Central

2015-01-01

We investigate the influence of structural heterogeneity on the transport properties of simple gases in a Hybrid Reverse Monte Carlo (HRMC) constructed model of silicon carbide-derived carbon (SiC-DC). The energy landscape of the system is determined based on free energy analysis of the atomistic model. The overall energy barriers of the system for different gases are computed along with important properties, such as Henry constant and differential enthalpy of adsorption at infinite dilution, and indicate hydrophobicity of the SiC-DC structure and its affinity for CO2 and CH4 adsorption. We also study the effect of molecular geometry, pore structure and energy heterogeneity considering different hopping scenarios for diffusion of CO2 and CH4 through ultramicropores using the Nudged Elastic Band (NEB) method. It is shown that the energy barrier of a hopping molecule is very sensitive to the shape of the pore entry. We provide evidence for the influence of structural heterogeneity on self-diffusivity of methane and carbon dioxide using molecular dynamics simulation, based on a maximum in the variation of self-diffusivity with loading. A comparison of the MD simulation results with self-diffusivities from quasi-elastic neutron scattering (QENS) measurements and, with macroscopic uptake-based low-density transport coefficients, reveals the existence of internal barriers not captured in MD simulation and QENS experiments. Nevertheless, the simulation and macroscopic uptake-based diffusion coefficients agree within a factor of 2–3, indicating that our HRMC model structure captures most of the important energy barriers affecting the transport of CH4 in the nanostructure of SiC-DC. PMID:24932319

Influence of Structural Heterogeneity on Diffusion of CH4 and CO2 in Silicon Carbide-Derived Nanoporous Carbon.

PubMed

Farmahini, Amir H; Shahtalebi, Ali; Jobic, Hervé; Bhatia, Suresh K

2014-06-05

We investigate the influence of structural heterogeneity on the transport properties of simple gases in a Hybrid Reverse Monte Carlo (HRMC) constructed model of silicon carbide-derived carbon (SiC-DC). The energy landscape of the system is determined based on free energy analysis of the atomistic model. The overall energy barriers of the system for different gases are computed along with important properties, such as Henry constant and differential enthalpy of adsorption at infinite dilution, and indicate hydrophobicity of the SiC-DC structure and its affinity for CO 2 and CH 4 adsorption. We also study the effect of molecular geometry, pore structure and energy heterogeneity considering different hopping scenarios for diffusion of CO 2 and CH 4 through ultramicropores using the Nudged Elastic Band (NEB) method. It is shown that the energy barrier of a hopping molecule is very sensitive to the shape of the pore entry. We provide evidence for the influence of structural heterogeneity on self-diffusivity of methane and carbon dioxide using molecular dynamics simulation, based on a maximum in the variation of self-diffusivity with loading. A comparison of the MD simulation results with self-diffusivities from quasi-elastic neutron scattering (QENS) measurements and, with macroscopic uptake-based low-density transport coefficients, reveals the existence of internal barriers not captured in MD simulation and QENS experiments. Nevertheless, the simulation and macroscopic uptake-based diffusion coefficients agree within a factor of 2-3, indicating that our HRMC model structure captures most of the important energy barriers affecting the transport of CH 4 in the nanostructure of SiC-DC.

Global methane emission estimates for 2000-2012 from CarbonTracker Europe-CH4 v1.0

NASA Astrophysics Data System (ADS)

Tsuruta, Aki; Aalto, Tuula; Backman, Leif; Hakkarainen, Janne; van der Laan-Luijkx, Ingrid T.; Krol, Maarten C.; Spahni, Renato; Houweling, Sander; Laine, Marko; Dlugokencky, Ed; Gomez-Pelaez, Angel J.; van der Schoot, Marcel; Langenfelds, Ray; Ellul, Raymond; Arduini, Jgor; Apadula, Francesco; Gerbig, Christoph; Feist, Dietrich G.; Kivi, Rigel; Yoshida, Yukio; Peters, Wouter

2017-03-01

We present a global distribution of surface methane (CH4) emission estimates for 2000-2012 derived using the CarbonTracker Europe-CH4 (CTE-CH4) data assimilation system. In CTE-CH4, anthropogenic and biospheric CH4 emissions are simultaneously estimated based on constraints of global atmospheric in situ CH4 observations. The system was configured to either estimate only anthropogenic or biospheric sources per region, or to estimate both categories simultaneously. The latter increased the number of optimizable parameters from 62 to 78. In addition, the differences between two numerical schemes available to perform turbulent vertical mixing in the atmospheric transport model TM5 were examined. Together, the system configurations encompass important axes of uncertainty in inversions and allow us to examine the robustness of the flux estimates. The posterior emission estimates are further evaluated by comparing simulated atmospheric CH4 to surface in situ observations, vertical profiles of CH4 made by aircraft, remotely sensed dry-air total column-averaged mole fraction (XCH4) from the Total Carbon Column Observing Network (TCCON), and XCH4 from the Greenhouse gases Observing Satellite (GOSAT). The evaluation with non-assimilated observations shows that posterior XCH4 is better matched with the retrievals when the vertical mixing scheme with faster interhemispheric exchange is used. Estimated posterior mean total global emissions during 2000-2012 are 516 ± 51 Tg CH4 yr-1, with an increase of 18 Tg CH4 yr-1 from 2000-2006 to 2007-2012. The increase is mainly driven by an increase in emissions from South American temperate, Asian temperate and Asian tropical TransCom regions. In addition, the increase is hardly sensitive to different model configurations ( < 2 Tg CH4 yr-1 difference), and much smaller than suggested by EDGAR v4.2 FT2010 inventory (33 Tg CH4 yr-1), which was used for prior anthropogenic emission estimates. The result is in good agreement with other

Highly Permeable AlPO-18 Membranes for N 2 /CH 4 Separation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zong, Zhaowang; Elsaidi, Sameh K.; Thallapally, Praveen K.

Herein we demonstrate that AlPO-18 membranes can separate N2/CH4 gas mixtures at unprecedented N2 permeances. The best membranes separated N2/CH4 mixtures with N2 permeances as high as 3076 GPU and separation selectivities as high as 4.6. Gas mixture separation data, N2 and CH4 adsorption isotherms, ideal adsorbed solution theory (IAST), and breakthrough experiments were collected to understand the separation mechanisms. Competitive adsorption and differences in diffusivities were identified as the prevailing separation mechanisms. Differences in diffusivity played a more dominant role than the competitive adsorption, and led to nitrogen selective membranes.

Physiology, biochemistry, and specific inhibitors of CH4, NH4+, and CO oxidation by methanotrophs and nitrifiers.

PubMed Central

Bédard, C; Knowles, R

1989-01-01

Ammonia oxidizers (family Nitrobacteraceae) and methanotrophs (family Methylococcaceae) oxidize CO and CH4 to CO2 and NH4+ to NO2-. However, the relative contributions of the two groups of organisms to the metabolism of CO, CH4, and NH4+ in various environments are not known. In the ammonia oxidizers, ammonia monooxygenase, the enzyme responsible for the conversion of NH4+ to NH2OH, also catalyzes the oxidation of CH4 to CH3OH. Ammonia monooxygenase also mediates the transformation of CH3OH to CO2 and cell carbon, but the pathway by which this is done is not known. At least one species of ammonia oxidizer, Nitrosococcus oceanus, exhibits a Km for CH4 oxidation similar to that of methanotrophs. However, the highest rate of CH4 oxidation recorded in an ammonia oxidizer is still five times lower than rates in methanotrophs, and ammonia oxidizers are apparently unable to grow on CH4. Methanotrophs oxidize NH4+ to NH2OH via methane monooxygenase and NH4+ to NH2OH via methane monooxygenase and NH2OH to NO2- via an NH2OH oxidase which may resemble the enzyme found in ammonia oxidizers. Maximum rates of NH4+ oxidation are considerably lower than in ammonia oxidizers, and the affinity for NH4+ is generally lower than in ammonia oxidizers. NH4+ does not apparently support growth in methanotrophs. Both ammonia monooxygenase and methane monooxygenase oxidize CO to CO2, but CO cannot support growth in either ammonia oxidizers or methanotrophs. These organisms have affinities for CO which are comparable to those for their growth substrates and often higher than those in carboxydobacteria. The methane monooxygenases of methanotrophs exist in two forms: a soluble form and a particulate form. The soluble form is well characterized and appears unrelated to the particulate. Ammonia monooxygenase and the particulate methane monooxygenase share a number of similarities. Both enzymes contain copper and are membrane bound. They oxidize a variety of inorganic and organic compounds, and

Methodological factors affecting gas and methane production during in vitro rumen fermentation evaluated by meta-analysis approach.

PubMed

Maccarana, Laura; Cattani, Mirko; Tagliapietra, Franco; Schiavon, Stefano; Bailoni, Lucia; Mantovani, Roberto

2016-01-01

Effects of some methodological factors on in vitro measures of gas production (GP, mL/g DM), CH4 production (mL/g DM) and proportion (% CH4 on total GP) were investigated by meta-analysis. These factors were considered: pressure in the GP equipment (0 = constant; 1 = increasing), incubation time (0 = 24; 1 = ≥ 48 h), time of rumen fluid collection (0 = before feeding; 1 = after feeding of donor animals), donor species of rumen fluid (0 = sheep; 1 = bovine), presence of N in the buffer solution (0 = presence; 1 = absence), and ratio between amount of buffered rumen fluid and feed sample (BRF/FS; 0 = ≤ 130 mL/g DM; 1 = 130-140 mL/g DM; 2 = ≥ 140 mL/g DM). The NDF content of feed sample incubated (NDF) was considered as a continuous variable. From an initial database of 105 papers, 58 were discarded because one of the above-mentioned factors was not stated. After discarding 17 papers, the final dataset comprised 30 papers (339 observations). A preliminary mixed model analysis was carried out on experimental data considering the study as random factor. Variables adjusted for study effect were analyzed using a backward stepwise analysis including the above-mentioned variables. The analysis showed that the extension of incubation time and reduction of NDF increased GP and CH4 values. Values of GP and CH4 also increased when rumen fluid was collected after feeding compared to before feeding (+26.4 and +9.0 mL/g DM, for GP and CH4), from bovine compared to sheep (+32.8 and +5.2 mL/g DM, for GP and CH4), and when the buffer solution did not contain N (+24.7 and +6.7 mL/g DM for GP and CH4). The increase of BRF/FS ratio enhanced GP and CH4 production (+7.7 and +3.3 mL/g DM per each class of increase, respectively). In vitro techniques for measuring GP and CH4 production are mostly used as screening methods, thus a full standardization of such techniques is not feasible. However, a greater harmonization

RKR Franck-Condon factors for blue and ultraviolet transitions of some molecules of astrophysical interest and some comments on the interstellar abundance of CH, CH+ and SiH+.

NASA Technical Reports Server (NTRS)

Liszt, H. S.; Hayden Smith, W.

1972-01-01

RKR Franck-Condon factors for thirteen of the blue and ultraviolet transitions of AlF, AlO, BH, BD, CH, CD, CH(+), SiO and SiH(+) have been calculated. The interstellar abundances of CH, CH(+) and SiH(+) are discussed with regard to recent laboratory measurements, our Franck-Condon factors, and observations of the sun and the interstellar medium.

Computing energy levels of CH4, CHD3, CH3D, and CH3F with a direct product basis and coordinates based on the methyl subsystem.

PubMed

Zhao, Zhiqiang; Chen, Jun; Zhang, Zhaojun; Zhang, Dong H; Wang, Xiao-Gang; Carrington, Tucker; Gatti, Fabien

2018-02-21

Quantum mechanical calculations of ro-vibrational energies of CH 4 , CHD 3 , CH 3 D, and CH 3 F were made with two different numerical approaches. Both use polyspherical coordinates. The computed energy levels agree, confirming the accuracy of the methods. In the first approach, for all the molecules, the coordinates are defined using three Radau vectors for the CH 3 subsystem and a Jacobi vector between the remaining atom and the centre of mass of CH 3 . Euler angles specifying the orientation of a frame attached to CH 3 with respect to a frame attached to the Jacobi vector are used as vibrational coordinates. A direct product potential-optimized discrete variable vibrational basis is used to build a Hamiltonian matrix. Ro-vibrational energies are computed using a re-started Arnoldi eigensolver. In the second approach, the coordinates are the spherical coordinates associated with four Radau vectors or three Radau vectors and a Jacobi vector, and the frame is an Eckart frame. Vibrational basis functions are products of contracted stretch and bend functions, and eigenvalues are computed with the Lanczos algorithm. For CH 4 , CHD 3 , and CH 3 D, we report the first J > 0 energy levels computed on the Wang-Carrington potential energy surface [X.-G. Wang and T. Carrington, J. Chem. Phys. 141(15), 154106 (2014)]. For CH 3 F, the potential energy surface of Zhao et al. [J. Chem. Phys. 144, 204302 (2016)] was used. All the results are in good agreement with experimental data.

Computing energy levels of CH4, CHD3, CH3D, and CH3F with a direct product basis and coordinates based on the methyl subsystem

NASA Astrophysics Data System (ADS)

Zhao, Zhiqiang; Chen, Jun; Zhang, Zhaojun; Zhang, Dong H.; Wang, Xiao-Gang; Carrington, Tucker; Gatti, Fabien

2018-02-01

Quantum mechanical calculations of ro-vibrational energies of CH4, CHD3, CH3D, and CH3F were made with two different numerical approaches. Both use polyspherical coordinates. The computed energy levels agree, confirming the accuracy of the methods. In the first approach, for all the molecules, the coordinates are defined using three Radau vectors for the CH3 subsystem and a Jacobi vector between the remaining atom and the centre of mass of CH3. Euler angles specifying the orientation of a frame attached to CH3 with respect to a frame attached to the Jacobi vector are used as vibrational coordinates. A direct product potential-optimized discrete variable vibrational basis is used to build a Hamiltonian matrix. Ro-vibrational energies are computed using a re-started Arnoldi eigensolver. In the second approach, the coordinates are the spherical coordinates associated with four Radau vectors or three Radau vectors and a Jacobi vector, and the frame is an Eckart frame. Vibrational basis functions are products of contracted stretch and bend functions, and eigenvalues are computed with the Lanczos algorithm. For CH4, CHD3, and CH3D, we report the first J > 0 energy levels computed on the Wang-Carrington potential energy surface [X.-G. Wang and T. Carrington, J. Chem. Phys. 141(15), 154106 (2014)]. For CH3F, the potential energy surface of Zhao et al. [J. Chem. Phys. 144, 204302 (2016)] was used. All the results are in good agreement with experimental data.

Thermal decomposition of ethanol. 4. Ab initio chemical kinetics for reactions of H atoms with CH3CH2O and CH3CHOH radicals.

PubMed

Xu, Z F; Xu, Kun; Lin, M C

2011-04-21

The potential energy surfaces of H-atom reactions with CH(3)CH(2)O and CH(3)CHOH, two major radicals in the decomposition and oxidation of ethanol, have been studied at the CCSD(T)/6-311+G(3df,2p) level of theory with geometric optimization carried out at the BH&HLYP/6-311+G(3df,2p) level. The direct hydrogen abstraction channels and the indirect association/decomposition channels from the chemically activated ethanol molecule have been considered for both reactions. The rate constants for both reactions have been calculated at 100-3000 K and 10(-4) Torr to 10(3) atm Ar pressure by microcanonical VTST/RRKM theory with master equation solution for all accessible product channels. The results show that the major product channel of the CH(3)CH(2)O + H reaction is CH(3) + CH(2)OH under atmospheric pressure conditions. Only at high pressure and low temperature, the rate constant for CH(3)CH(2)OH formation by collisonal deactivation becomes dominant. For CH(3)CHOH + H, there are three major product channels; at high temperatures, CH(3)+CH(2)OH production predominates at low pressures (P < 100 Torr), while the formation of CH(3)CH(2)OH by collisional deactivation becomes competitive at high pressures and low temperatures (T < 500 K). At high temperatures, the direct hydrogen abstraction reaction producing CH(2)CHOH + H(2) becomes dominant. Rate constants for all accessible product channels in both systems have been predicted and tabulated for modeling applications. The predicted value for CH(3)CHOH + H at 295 K and 1 Torr pressure agrees closely with available experimental data. For practical modeling applications, the rate constants for the thermal unimolecular decomposition of ethanol giving key accessible products have been predicted; those for the two major product channels taking place by dehydration and C-C breaking agree closely with available literature data.

Insights into the structure of mixed CO 2/CH 4 in gas hydrates

DOE PAGES

Everett, S. Michelle; Rawn, Claudia J.; Chakoumakos, Bryan C.; ...

2015-05-12

The exchange of carbon dioxide for methane in natural gas hydrates is an attractive approach to harvesting CH 4 for energy production while simultaneously sequestering CO 2. In addition to the energy and environmental implications, the solid solution of clathrate hydrate (CH 4) 1-x(CO 2) x·5.75H 2O provides a model system to study how the distinct bonding and shapes of CH 4 and CO 2 influence the structure and properties of the compound. In this paper, high-resolution neutron diffraction was used to examine mixed CO 2/CH 4 gas hydrates. CO 2-rich hydrates had smaller lattice parameters, which were attributed tomore » the higher affinity of the CO 2 molecule interacting with H 2O molecules that form the surrounding cages, and resulted in a reduction in the unit-cell volume. Experimental nuclear scattering densities illustrate how the cage occupants and energy landscape change with composition. Finally, these results provide important insights on the impact and mechanisms for the structure of mixed CH 4/CO 2 gas hydrate.« less

Rate Coefficient Measurements of the Reaction CH3 + O2 = CH3O + O

NASA Technical Reports Server (NTRS)

Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

1999-01-01

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, sub -0.47 ) x 10(exp 13) e(-15813 +/- 587 K/T)/cubic cm.mol.s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

Rate Coefficient Measurements of the Reaction CH3+O2+CH3O+O

NASA Technical Reports Server (NTRS)

Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

1999-01-01

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, -0.47)) X 10(exp 13) exp(- 15813 +/- 587 K/T)cc/mol s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

C-H bond functionalization via hydride transfer: formation of α-arylated piperidines and 1,2,3,4-tetrahydroisoquinolines via stereoselective intramolecular amination of benzylic C-H bonds.

PubMed

Vadola, Paul A; Carrera, Ignacio; Sames, Dalibor

2012-08-17

We here report a study of the intramolecular amination of sp(3) C-H bonds via the hydride transfer cyclization of N-tosylimines (HT-amination). In this transformation, 5-aryl aldehydes are subjected to N-toluenesulfonamide in the presence of BF(3)·OEt(2) to effect imine formation and HT-cyclization, leading to 2-arylpiperidines and 3-aryl-1,2,3,4-tetrahydroisoquinolines in a one-pot procedure. We examined the reactivity of a range of aldehyde substrates as a function of their conformational flexibility. Substrates of higher conformational rigidity were more reactive, giving higher yields of the desired products. However, a single substituent on the alkyl chain linking the N-tosylimine and the benzylic sp(3) C-H bonds was sufficient for HT-cyclization to occur. In addition, an examination of various arenes revealed that the electronic character of the hydridic C-H bonds dramatically affects the efficiency of the reaction. We also found that this transformation is highly stereoselective; 2-substituted aldehydes yield cis-2,5-disubstituted piperidines, while 3-substituted aldehydes afford trans-2,4-disubstituted piperidines. The stereoselectivity is a consequence of thermodynamic control. The pseudoallylic strain between the arene and tosyl group on the piperidine ring is proposed to rationalize the greater stability of the isomer with the aryl ring in the axial position. This preferential placement of the arene is proposed to affect the observed stereoselectivity.

C-H Bond Functionalization via Hydride Transfer: Formation of α-Arylated Piperidines and 1,2,3,4-Tetrahydroisoquinolines via Stereoselective Intramolecular Amination of Benzylic C-H Bonds

PubMed Central

Vadola, Paul A.; Carrera, Ignacio; Sames, Dalibor

2012-01-01

We here report a study of the intramolecular amination of sp3 C-H bonds via the hydride transfer cyclization of N-tosylimines (HT-amination). In this transformation, 5-aryl-aldehydes are subjected to N-toluenesulfonamide in the presence of BF3•OEt2 to effect imine formation and HT-cyclization, leading to 2-aryl-piperidines and 3-aryl-1,2,3,4-tetrahydroisoquinolines in a one-pot procedure. We examined the reactivity of a range of aldehyde substrates as a function of their conformational flexibility. Substrates of higher conformational rigidity were more reactive, giving higher yields of the desired products. However, a single substituent on the alkyl chain linking the N-tosylimine and the benzylic sp3 C-H bonds was sufficient for HT-cyclization to occur. In addition, an examination of various arenes revealed that the electronic character of the hydridic C-H bonds dramatically affects the efficiency of the reaction. We also found that this transformation is highly stereoselective; 2-substituted aldehydes yield cis-2,5-disubstituted piperidines, while 3-substituted aldehydes afford trans-2,4-disubstituted piperidines. The stereoselectivity is a consequence of thermodynamic control. The pseudo-allylic strain between the arene and tosyl group on the piperidine ring is proposed to rationalize the greater stability of the isomer with the aryl ring in the axial position. This preferential placement of the arene is proposed to affect the observed stereoselectivity. PMID:22672002

A process-based inventory model for landfill CH4 emissions inclusive of seasonal soil microclimate and CH4 oxidation

USDA-ARS?s Scientific Manuscript database

We have developed and field-validated an annual inventory model for California landfill CH4 emissions that incorporates both site-specific soil properties and soil microclimate modeling coupled to 0.5o scale global climatic models. Based on 1-D diffusion, CALMIM (California Landfill Methane Inventor...

Reflected shock tube studies of high-temperature rate constants for OH + CH4 --> CH3 + H2O and CH3 + NO2 --> CH3O + NO.

PubMed

Srinivasan, N K; Su, M-C; Sutherland, J W; Michael, J V

2005-03-10

The reflected shock tube technique with multipass absorption spectrometric detection of OH radicals at 308 nm has been used to study the reactions OH + CH(4) --> CH(3) + H(2)O and CH(3) + NO(2) --> CH(3)O + NO. Over the temperature range 840-2025 K, the rate constants for the first reaction can be represented by the Arrhenius expression k = (9.52 +/- 1.62) x 10(-11) exp[(-4134 +/- 222 K)/T] cm(3) molecule(-1) s(-1). Since this reaction is important in both combustion and atmospheric chemistry, there have been many prior investigations with a variety of techniques. The present results extend the temperature range by 500 K and have been combined with the most accurate earlier studies to derive an evaluation over the extended temperature range 195-2025 K. A three-parameter expression describes the rate behavior over this temperature range, k = (1.66 x 10(-18))T(2.182) exp[(-1231 K)/T] cm(3) molecule(-1) s(-1). Previous theoretical studies are discussed, and the present evaluation is compared to earlier theoretical estimates. Since CH(3) radicals are a product of the reaction and could cause secondary perturbations in rate constant determinations, the second reaction was studied by OH radical production from the fast reactions CH(3)O --> CH(2)O + H and H + NO(2) --> OH + NO. The measured rate constant is 2.26 x 10(-11) cm(3) molecule(-1) s(-1) and is not dependent on temperature from 233 to 1700 K within experimental error.

[Spatiotemporal variations of natural wetland CH4 emissions over China under future climate change].

PubMed

Liu, Jian-gong; Zhu, Qiu-an; Shen, Yan; Yang, Yan-zheng; Luo, Yun-peng; Peng, Chang-hui

2015-11-01

Based on a new process-based model, TRIPLEX-GHG, this paper analyzed the spatio-temporal variations of natural wetland CH4 emissions over China under different future climate change scenarios. When natural wetland distributions were fixed, the amount of CH4 emissions from natural wetland ecosystem over China would increase by 32.0%, 55.3% and 90.8% by the end of 21st century under three representative concentration pathways (RCPs) scenarios, RCP2. 6, RCP4.5 and RCP8.5, respectively, compared with the current level. Southern China would have higher CH4 emissions compared to that from central and northern China. Besides, there would be relatively low emission fluxes in western China while relatively high emission fluxes in eastern China. Spatially, the areas with relatively high CH4 emission fluxes would be concentrated in the middle-lower reaches of the Yangtze River, the Northeast and the coasts of the Pearl River. In the future, most natural wetlands would emit more CH4 for RCP4.5 and RCP8.5 than that of 2005. However, under RCP2.6 scenario, the increasing trend would be curbed and CH4 emissions (especially from the Qinghai-Tibet Plateau) begin to decrease in the late 21st century.

Biogeochemical controls on microbial CH4 and CO2 production in Arctic polygon tundra

NASA Astrophysics Data System (ADS)

Zheng, J.

2016-12-01

Accurately simulating methane (CH4) and carbon dioxide (CO2) emissions from high latitude soils is critically important for reducing uncertainties in soil carbon-climate feedback predictions. The signature polygonal ground of Arctic tundra generates high level of heterogeneity in soil thermal regime, hydrology and oxygen availability, which limits the application of current land surface models with simple moisture response functions. We synthesized CH4 and CO2 production measurements from soil microcosm experiments across a wet-to dry permafrost degradation gradient from low-centered (LCP) to flat-centered (FCP), and high-centered polygons (HCP) to evaluate the relative importance of biogeochemical processes and their response to warming. More degraded polygon (HCP) showed much less carbon loss as CO2 or CH4, while the total CO2 production from FCP is comparable to that from LCP. Maximum CH4 production from the active layer of LCP was nearly 10 times that of permafrost and FCP. Multivariate analyses identifies gravimetric water content and organic carbon content as key predictors for CH4 production, and iron reduction as a key regulator of pH. The synthesized data are used to validate the geochemical model PHREEQC with extended anaerobic organic substrate turnover, fermentation, iron reduction, and methanogenesis reactions. Sensitivity analyses demonstrate that better representations of anaerobic processes and their pH dependency could significantly improve estimates of CH4 and CO2 production. The synthesized data suggest local decreases in CH4 production along the polygon degradation gradient, which is consistent with previous surface flux measurements. Methane oxidation occurring through the soil column of degraded polygons contributes to their low CH4 emissions as well.

Version 1.3 AIM SOFIE measured methane (CH4): Validation and seasonal climatology

NASA Astrophysics Data System (ADS)

Rong, P. P.; Russell, J. M.; Marshall, B. T.; Siskind, D. E.; Hervig, M. E.; Gordley, L. L.; Bernath, P. F.; Walker, K. A.

2016-11-01

The V1.3 methane (CH4) measured by the Aeronomy of Ice in the Mesosphere (AIM) Solar Occultation for Ice Experiment (SOFIE) instrument is validated in the vertical range of 25-70 km. The random error for SOFIE CH4 is 0.1-1% up to 50 km and degrades to 9% at ˜ 70 km. The systematic error remains at 4% throughout the stratosphere and lower mesosphere. Comparisons with CH4 data taken by the SCISAT Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS) and the Envisat Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) show an agreement within 15% in the altitude range 30-60 km. Below 25 km SOFIE CH4 is systematically higher (≥20%), while above 65 km it is lower by a similar percentage. The sign change from the positive to negative bias occurs between 55 km and 60 km (or 40 km and 45 km) in the Northern (or Southern) Hemisphere. Methane, H2O, and 2CH4 + H2O yearly differences from their values in 2009 are examined using SOFIE and MIPAS CH4 and the Aura Microwave Limb Sounder (MLS) measured H2O. It is concluded that 2CH4 + H2O is conserved with altitude up to an upper limit between 35 km and 50 km depending on the season. In summer this altitude is higher. In the Northern Hemisphere the difference relative to 2009 is the largest in late spring and the established difference prevails throughout summer and fall, suggesting that summer and fall are dynamically quiet. In both hemispheres during winter there are disturbances (with a period of 1 month) that travel downward throughout the stratosphere with a speed similar to the winter descent.

Role of plant-mediated gas transport in CH4 emissions from Phragmites-dominated peatlands

NASA Astrophysics Data System (ADS)

van den Berg, Merit; Ingwersen, Joachim; van den Elzen, Eva; Lamers, Leon P. M.; Streck, Thilo

2016-04-01

A large part of the methane (CH4) produced in peatlands is directly oxidized and the extent of its oxidation depends on the gas transport pathway. In wetland ecosystems, CH4 can be transported from the soil to the atmosphere via diffusion, ebullition and via aerenchyma of roots and stems of vascular plants. Compared to other wetland plants, the very common species Phragmites australis (Common reed) appears to have a high ability to transport gases between the soil and atmosphere. The gas exchange within Phragmites plants takes place via convective flow through the culm, which is believed to be achieved by a humidity-induced pressure gradient and is more than 5-times as efficient as diffusion. By this mechanism, CH4 surpasses the upper (oxic) soil layers and therefore oxidation of CH4 may well be reduced. On the other hand, transport of oxygen in Phragmites plants tends to enhance O2concentration in the rhizosphere, which will foster CH4oxidation in deeper soil layers. It is therefore unknown whether humidity-induced convection leads to higher or lower overall CH4 emission in Phragmites, which is essential to understand their role in the emissions from these very common peatland types. To investigate whether this internal gas transport mechanism of reed promotes or reduces CH4 fluxes to the atmosphere, we conducted manipulative field experiments in a large Phragmites peatland in South-West Germany in October 2014 and July 2015. Using large chambers, we compared CH4 fluxes from intact plots, plots with cut reed, and plots with cut + sealed reed to exclude gas transport through the plants. Additionally, pore water samples from the plots were analyzed for possible changes in soil chemistry due to the change of oxygen transport into the soil by the treatments. Based on our results, we will explain the potential role of rhizosphere oxygenation and convective flow on CH4 emissions from Phragmites-dominated peatlands in relation to other environmental condition.

Molecular simulation of CO2/CH4 adsorption in brown coal: Effect of oxygen-, nitrogen-, and sulfur-containing functional groups

NASA Astrophysics Data System (ADS)

Dang, Yong; Zhao, Lianming; Lu, Xiaoqing; Xu, Jing; Sang, Pengpeng; Guo, Sheng; Zhu, Houyu; Guo, Wenyue

2017-11-01

The CO2/CH4 adsorption behaviors in brown coal at the temperatures of 298, 313, and 373 K and in the pressure range of 0.005-10 MPa were investigated by molecular dynamics (MD), density functional theory (DFT), and grand canonical Monte Carlo (GCMC) simulations. The absolute adsorption isotherms of single-component CH4 and CO2 exhibit type-I Langmuir adsorption behavior showing a negative influence of temperature. For the binary CO2/CH4 mixture, brown coal shows super high selectivity of CO2 over CH4 at pressures below 0.2 MPa, which then decreases quickly and finally tends to be constant when the pressure increases. The high competitive adsorption of CO2 originates from the effects of (i) the large electrostatic contributions, (ii) the conducive micropore environment with pore sizes below 0.56 nm, and (iii) the stronger adsorption of CO2 with respect to CH4. These effects are strengthened by the high-density oxygen-containing, pyridine, and thiophene functional groups contained in brown coal, which provide abundant and strong adsorption sites for CO2, but show weaker affinity to CH4. Furthermore, the influence of various nitrogen- and sulfur-containing functional groups on the CO2 adsorption capacity was also investigated. The results indicate that the basicity of the oxygen- and nitrogen-containing groups has a large influence on the CO2 adsorption, while for the sulfur functional groups the determining factor is the polarity.

Year-round measurements of CH4 exchange in a forested drained peatland using automated chambers

NASA Astrophysics Data System (ADS)

Korkiakoski, Mika; Koskinen, Markku; Penttilä, Timo; Arffman, Pentti; Ojanen, Paavo; Minkkinen, Kari; Laurila, Tuomas; Lohila, Annalea

2016-04-01

Pristine peatlands are usually carbon accumulating ecosystems and sources of methane (CH4). Draining peatlands for forestry increases the thickness of the oxic layer, thus enhancing CH4 oxidation which leads to decreased CH4 emissions. Closed chambers are commonly used in estimating the greenhouse gas exchange between the soil and the atmosphere. However, the closed chamber technique alters the gas concentration gradient making the concentration development against time non-linear. Selecting the correct fitting method is important as it can be the largest source of uncertainty in flux calculation. We measured CH4 exchange rates and their diurnal and seasonal variations in a nutrient-rich drained peatland located in southern Finland. The original fen was drained for forestry in 1970s and now the tree stand is a mixture of Scots pine, Norway spruce and Downy birch. Our system consisted of six transparent polycarbonate chambers and stainless steel frames, positioned on different types of field and moss layer. During winter, the frame was raised above the snowpack with extension collars and the height of the snowpack inside the chamber was measured regularly. The chambers were closed hourly and the sample gas was sucked into a cavity ring-down spectrometer and analysed for CH4, CO2 and H2O concentration with 5 second time resolution. The concentration change in time in the beginning of a closure was determined with linear and exponential fits. The results show that linear regression systematically underestimated the CH4 flux when compared to exponential regression by 20-50 %. On the other hand, the exponential regression seemed not to work reliably with small fluxes (< 3.5 μg CH4 m-2 h-1): using exponential regression in such cases typically resulted in anomalously large fluxes and high deviation. Due to these facts, we recommend first calculating the flux with the linear regression and, if the flux is high enough, calculate the flux again using the exponential

Selective Adsorption and Selective Transport Diffusion of CO2-CH4 Binary Mixture in Coal Ultramicropores.

PubMed

Zhao, Yongliang; Feng, Yanhui; Zhang, Xinxin

2016-09-06

The adsorption and diffusion of the CO2-CH4 mixture in coal and the underlying mechanisms significantly affect the design and operation of any CO2-enhanced coal-bed methane recovery (CO2-ECBM) project. In this study, bituminous coal was fabricated based on the Wiser molecular model and its ultramicroporous parameters were evaluated; molecular simulations were established through Grand Canonical Monte Carlo (GCMC) and Molecular Dynamic (MD) methods to study the effects of temperature, pressure, and species bulk mole fraction on the adsorption isotherms, adsorption selectivity, three distinct diffusion coefficients, and diffusivity selectivity of the binary mixture in the coal ultramicropores. It turns out that the absolute adsorption amount of each species in the mixture decreases as temperature increases, but increases as its own bulk mole fraction increases. The self-, corrected, and transport diffusion coefficients of pure CO2 and pure CH4 all increase as temperature or/and their own bulk mole fractions increase. Compared to CH4, the adsorption and diffusion of CO2 are preferential in the coal ultramicropores. Adsorption selectivity and diffusivity selectivity were simultaneously employed to reveal that the optimal injection depth for CO2-ECBM is 800-1000 m at 308-323 K temperature and 8.0-10.0 MPa.

Real-time analysis of δ13C- and δD-CH4 by high precision laser spectroscopy

NASA Astrophysics Data System (ADS)

Eyer, Simon; Emmenegger, Lukas; Tuzson, Béla; Fischer, Hubertus; Mohn, Joachim

2014-05-01

Methane (CH4) is the most important non-CO2 greenhouse gas (GHG) contributing 18% to total radiative forcing. Anthropogenic sources (e.g. ruminants, landfills) contribute 60% to total emissions and led to an increase in its atmospheric mixing ratio from 700 ppb in pre-industrial times to 1819 ± 1 ppb in 2012 [1]. Analysis of the most abundant methane isotopologues 12CH4, 13CH4 and 12CH3D can be used to disentangle the various source/sink processes [2] and to develop target oriented reduction strategies. High precision isotopic analysis of CH4 can be accomplished by isotope-ratio mass-spectrometry (IRMS) [2] and more recently by mid-infrared laser-based spectroscopic techniques. For high precision measurements in ambient air, however, both techniques rely on preconcentration of the target gas [3]. In an on-going project, we developed a fully-automated, field-deployable CH4 preconcentration unit coupled to a dual quantum cascade laser absorption spectrometer (QCLAS) for real-time analysis of CH4 isotopologues. The core part of the rack-mounted (19 inch) device is a highly-efficient adsorbent trap attached to a motorized linear drive system and enclosed in a vacuum chamber. Thereby, the adsorbent trap can be decoupled from the Stirling cooler during desorption for fast desorption and optimal heat management. A wide variety of adsorbents, including: HayeSep D, molecular sieves as well as the novel metal-organic frameworks and carbon nanotubes were characterized regarding their surface area, isosteric enthalpy of adsorption and selectivity for methane over nitrogen. The most promising candidates were tested on the preconcentration device and a preconcentration by a factor > 500 was obtained. Furthermore analytical interferants (e.g. N2O, CO2) are separated by step-wise desorption of trace gases. A QCL absorption spectrometer previously described by Tuzson et al. (2010) for CH4 flux measurements was modified to obtain a platform for high precision and simultaneous

An estimate of the PH3, CH3D, and GeH4 abundances on Jupiter from the Voyager IRIS data at 4.5 microns

NASA Technical Reports Server (NTRS)

Drossart, P.; Encrenaz, T.; Combes, M.; Kunde, V.; Hanel, R.

1982-01-01

No evidence is found for large scale phosphine abundance variations over Jovian latitudes between -30 and +30 deg, in PH3, CH3D, and GeH4 abundances derived from the 2100-2250/cm region of the Voyager 1 IRIS spectra. The PH3/H2 value of (4.5 + or - 1.5) X 10 to the -7th derived from atmospheric regions corresponding to 170-200 K is 0.75 + or - 0.25 times the solar value, and suggests that the PH3/H2 ratio on Jupiter decreases with atmospheric pressure upon comparison with other PH3 determinations at 10 microns. In the 200-250 K region, CH3D/H2 and GeH4/H2 ratios of 2.0 X 10 to the -7th and 1.0 X 10 to the -9th, respectively, are derived within a factor of 2.0. Assuming a C/H value of 0.001, as derived from Voyager, the CH3D/H2 ratio obtained in this study implies a D/H ratio of 0.000018. This is in agreement with the interstellar medium value.

Low-Temperature Rate Coefficients of C2H with CH4 and CD4 from 154 to 359 K

NASA Technical Reports Server (NTRS)

Opansky, Brian J.; Leone, Stephen R.

1996-01-01

Rate coefficients for the reaction C2H + CH4 yields C2H2 + CH3 and C2H + CD4 yields C2HD + CD3 are measured over the temperature range 154-359 K using transient infrared laser absorption spectroscopy. Ethynyl radicals are produced by pulsed laser photolysis of C2H2 in a variable temperature flow cell, and a tunable color center laser probes the transient removal of C2H (Chi(exp 2) Sigma(+) (0,0,0)) in absorption. The rate coefficients for the reactions of C2H with CH4 and CD4 both show a positive temperature dependence over the range 154-359 K, which can be expressed as k(sub CH4) = (1.2 +/- 0.1) x 10(exp -11) exp((-491 +/- 12)/T) and k(sub CD4) = (8.7 +/- 1.8) x 10(exp -12) exp((-650 +/- 61)/T) cm(exp 3) molecule(exp -1) s(exp -1), respectively. The reaction of C2H + CH4 exhibits a significant kinetic isotope effect at 300 K of k(sub CH4)/k(sub CD4) = 2.5 +/- 0.2. Temperature dependent rate constants for C2H + C2H2 were also remeasured over an increased temperature range from 143 to 359 K and found to show a slight negative temperature dependence, which can be expressed as k(sub C2H2) = 8.6 x 10(exp -16) T(exp 1.8) exp((474 +/- 90)/T) cm(exp 3) molecule(exp -1) s(exp -1).

Large CO2 and CH4 release from a flooded formerly drained fen

NASA Astrophysics Data System (ADS)

Sachs, T.; Franz, D.; Koebsch, F.; Larmanou, E.; Augustin, J.

2016-12-01

Drained peatlands are usually strong carbon dioxide (CO2) sources. In Germany, up to 4.5 % of the national CO2 emissions are estimated to be released from agriculturally used peatlands and for some peatland-rich northern states, such as Mecklenburg-Western Pomerania, this share increases to about 20%. Reducing this CO2 source and restoring the peatlands' natural carbon sink is one objective of large-scale nature protection and restoration measures, in which 37.000 ha of drained and degraded peatlands in Mecklenburg-Western Pomerania are slated for rewetting. It is well known, however, that in the initial phase of rewetting, a reduction of the CO2 source strength is usually accompanied by an increase in CH4 emissions. Thus, whether and when the intended effects of rewetting with regard to greenhouse gases are achieved, depends on the balance of CO2 and CH4 fluxes and on the duration of the initial CH4 emission phase. In 2013, a new Fluxnet site went online at a flooded formerly drained river valley fen site near Zarnekow, NE Germany (DE-Zrk), to investigate the combined CO2 and CH4 dynamics at such a heavily degraded and rewetted peatland. The site is dominated by open water with submerged and floating vegetation and surrounding Typha latifolia.Nine year after rewetting, we found large CH4 emissions of 53 g CH4 m-2 a-1 from the open water area, which are 4-fold higher than from the surrounding vegetation zone (13 g CH4 m-2 a-1). Surprisingly, both the open water and the vegetated area were net CO2 sources of 158 and 750 g CO2 m-2 a-1, respectively. Unusual meteorological conditions with a warm and dry summer and a mild winter might have facilitated high respiration rates, particularly from temporally non-inundated organic mud in the vegetation zone.

Investigation of Wyoming Bentonite Hydration in Dry to Water-Saturated Supercritical CH4 and CH4/CO2 Mixtures: Implications for CO2-Enhanced Gas Production

NASA Astrophysics Data System (ADS)

Loring, J.

2015-12-01

Injection of CO2 into low permeability shale formations leads to additional gas recovery and reduces the flux of CO2 into the atmosphere, thus combining a strong economic incentive with a permanent storage option for CO2. Reduced formation transmissivity due to clay swelling is a concern in CO2-enhanced gas production. Clay minerals partly determine the physical (i.e. permeability, brittleness) and certain chemical properties (i.e. wetting ability, gas adsorption) of shales, and montmorillonites are of particular interest because they swell by the uptake of species in their interlayer. In this study, the hydration and expansion of Na-, Cs-, and NH4+-saturated montmorillonite (Na-, Cs-, and NH4-SWy-2) in high-pressure (90 bar) and moderate temperature (50 °C) methane, carbon dioxide, and CO2/CH4 mixtures (3 and 25 mole% CO2) were investigated using in situ IR spectroscopic titrations, in situ XRD, in situ MAS-NMR, and ab initio electronic structure calculations. The overarching goal was to better understand the hydration/expansion behavior of Na-SWy-2 in CO2/CH4 fluid mixtures by comparison to Cs-, and NH4+-saturated clays. Specific aims were to (1) determine if CH4 intercalates the clays, (2) probe the effects of increasing dissolved CO2 and H2O concentrations, and (3) understand the role of cation solvation by H2O and/or CO2. In pure CH4, no evidence of CH4 intercalation was detected by IR for any of the clays. Similarly, no measurable changes to the basal spacing were observed by XRD in the presence of pure CH4. However, when dry Cs- and NH4-SWy-2 were exposed to dry fluids containing CO2, IR showed maximum CO2 penetrated the interlayer, XRD indicated the clays expanded, and NMR showed evidence for cation solvation by CO2, in line with theoretical predictions. IR titration of these clays with water showed sorbed H2O concentrations decreased with increasing dissolved CO2, suggesting competition for interlayer residency by CO2 and H2O. For Na-SWy-2, on the other

Real-time observation of formation and relaxation dynamics of NH4 in (CH3OH)m(NH3)n clusters.

PubMed

Yamada, Yuji; Nishino, Yoko; Fujihara, Akimasa; Ishikawa, Haruki; Fuke, Kiyokazu

2009-03-26

The formation and relaxation dynamics of NH4(CH3OH)m(NH3)n clusters produced by photolysis of ammonia-methanol mixed clusters has been observed by a time-resolved pump-probe method with femtosecond pulse lasers. From the detailed analysis of the time evolutions of the protonated cluster ions, NH4(+)(CH3OH)m(NH3)n, the kinetic model has been constructed, which consists of sequential three-step reaction: ultrafast hydrogen-atom transfer producing the radical pair (NH4-NH2)*, the relaxation process of radical-pair clusters, and dissociation of the solvated NH4 clusters. The initial hydrogen transfer hardly occurs between ammonia and methanol, implying the unfavorable formation of radical pair, (CH3OH2-NH2)*. The remarkable dependence of the time constants in each step on the number and composition of solvents has been explained by the following factors: hydrogen delocalization within the clusters, the internal conversion of the excited-state radical pair, and the stabilization of NH4 by solvation. The dependence of the time profiles on the probe wavelength is attributed to the different ionization efficiency of the NH4(CH3OH)m(NH3)n clusters.

Reducing CH4 emission from rice paddy fields by altering water management

NASA Astrophysics Data System (ADS)

Sudo, S.; Itoh, M.

2010-12-01

Percentage of atmospheric methane emitted form rice paddy is estimated at 60Tg/yr (20 - 100Tg/yr) which is near 10% of total global methane emission of 535Tg/yr (410 - 660Tg) (IPCC(1995), and which is near 30% of anthropogenic CH4 emission. Thus, mitigation of CH4 emission is urgently required. CH4 in paddy soil is emanated by the activities of anaerobic bacteria which is called methane producer through reduction of CO2 or decomposition of acetic acid, and it is transported to atmosphere through soil or paddy water surface. It is effective to control methane emission from rice paddy that period is extended on intermittent drainage, composted rice straw is incorporated as fertilizer instead of flesh one, or other. However, empirical approach of these kinds of experiments had not been sufficient because such a kind of experiment required significant times and efforts. In this study, we conducted demonstrative experiments to verify the effects of water management method differences in order to reduce CH4 emission from rice paddy at 9 experimental sites in 8 prefectures. In this, we used new gas analyzer which can measure CH4, CO2 and N2O at once developed by National Institute for Agro-Environmental Sciences (NIAES), Japan. In this report, we show the results in two years of this study. 'Nakaboshi' (mid-season-drainage) is one of cultivation methods in rice paddy that surface water in paddy field is once drained for about 10 days and the field is maintained like upland field to give adequate stress to rice plant for better harvest qualities and yields. Our targeted evaluation was dependencies of Nakaboshi periods lengths and Nakaboshi periods to CH4 emission reduction amounts for total cultivation periods within harvest yield maintained. The longer length of Nakaboshi period was extended, the lesser CH4 emitted even after when Nakaboshi period lasted, as a whole. In some cases, for example in Kagoshima, exceptional phenomena of that significant high emission were

Electron-spin-resonance studies of 12CH3F + , 13CH3F + , and 12CH2DF + in neon matrices at 4 K: Comparison with theoretical calculations

NASA Astrophysics Data System (ADS)

Knight, Lon B., Jr.; Gregory, Brian W.; Hill, Devon W.; Arrington, C. A.; Momose, Takamasa; Shida, Tadamasa

1991-01-01

Various isotopic forms of the methyl fluoride cation 12CH3F+, 13CH3F+, and 12CH2DF+ have been generated by photoionization at 16.8 eV and separately by electron bombardment at 50 eV. The first electron-spin-resonance (ESR) results are reported for this radical cation which was isolated in neon matrices at 4 K. The measured A tensors or nuclear hyperfine parameters were compared with the results obtained from various computational approaches. Surprising observations were the large amounts of spin density on the methyl group, especially the hydrogen atoms, and the extreme differences in the deuterated spectra compared to the nondeuterated case. The presence of a single D atom apparently acts to prevent dynamic Jahn-Teller averaging which makes the methyl hydrogens equivalent on the ESR time scale. Such a dramatic Jahn-Teller effect has been previously observed for the similar methane cations CH+4 and CH2D+2. The magnetic parameters for CH2DF+ in neon at 4 K are gX=2.0032(5), gY=2.0106(8), and gZ=2.0120(5); for H: AX = 483(1), AY=476(1), and AZ=483(1) MHz; for D: ‖AX‖=5.0(3), ‖AY‖<3, and ‖AZ‖=7.1(3) MHz; for 19F : AX=965(1), AY=-130(2), and AZ=-166(1) MHz. For CH3F+, the g tensor and 19F A tensor were similar to those above but the H atoms were equivalent with values of AX=317(1), AY=323(2), and AZ=312 MHz.

CH{sub 4} and N{sub 2}O emissions from China’s beef feedlots with ad libitum and restricted feeding in fall and spring seasons

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lin, Zhi; Liao, Wenhua; Yang, Yuanyuan

Accurately quantifying methane (CH{sub 4}) and nitrous oxide (N{sub 2}O) emissions from beef operations in China is necessary to evaluate the contribution of beef cattle to greenhouse gas budgets at the national and global level. Methane and N{sub 2}O emissions from two intensive beef feedlots in the North China Plain, one with a restricted feeding strategy and high manure collection frequency and the other with an ad libitum feeding strategy and low manure collection frequency, were quantified in the fall and spring seasons using an inverse dispersion technique. The diel pattern of CH{sub 4} from the beef feedlot with anmore » ad libitum feed strategy (single peak during a day) differed from that under a restricted feeding condition (multiple peaks during a day), but little difference in the diel pattern of N{sub 2}O emissions between two feeding strategies was observed. The two-season average CH{sub 4} emission rates of the two intensive feedlots were 230 and 198 g CH{sub 4} animal{sup −1} d{sup −1} and accounted for 6.7% and 6.8% of the gross energy intake, respectively, indicating little impact of the feeding strategy and manure collection frequency on the CH{sub 4} conversion factor at the feedlot level. However, the average N{sub 2}O emission rates (21.2 g N{sub 2}O animal{sup −1} d{sup −1}) and conversion factor (8.5%) of the feedlot with low manure collection frequency were approximately 131% and 174% greater, respectively, than the feedlot under high frequency conditions, which had a N{sub 2}O emission rate and conversion factor of 9.2 g N{sub 2}O animal{sup −1} d{sup −1} and 3.1%, respectively, indicating that increasing manure collection frequency played an important role in reducing N{sub 2}O emissions from beef feedlots. In addition, comparison indicated that China’s beef and dairy cattle in feedlots appeared to have similar CH{sub 4} conversion factors. - Highlights: • CH{sub 4} and N{sub 2}O emissions from China’s beef feedlots

SAPO-34 Membranes for N-2/CH4 separation: Preparation, characterization, separation performance and economic evaluation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, SG; Zong, ZW; Zhou, SJ

2015-08-01

SAPO-34 membranes were synthesized by several routes towards N-2/CH4 separation. Membrane synthesis parameters including water content in the gel, crystallization time, support pore size, and aluminum source were investigated. High performance N-2-selective membranes were obtained on 100-nm-pore alumina tubes by using Al(i-C3H7O)(3) as aluminum source with a crystallization time of 6 h. These membranes separated N-2 from CH, with N-2 permeance as high as 500 GPU with separation selectivity of 8 at 24 degrees C. for a 50/50 N-2/CH4 mixture. Nitrogen and CH, adsorption isotherms were measured on SAPO-34 crystals. The N-2 and CH, heats of adsorption were 11 andmore » 15 kJ/mol, respectively, which lead to a preferential adsorption of CE-H-4 over N-2 in the N-2/CH4 mixture. Despite this, the SAPO-34 membranes were selective for N-2 over CH4 in the mixture because N-2 diffuses much faster than CH4 and differences in diffusivity played a more critical role than the competitive adsorption. Preliminary economic evaluation indicates that the required N-2/CH4 selectivity would be 15 in order to maintain a CH4 loss below 10%. For small nitrogen-contaminated gas wells, our current SAPO-34 membranes have potential to compete with the benchmark technology cryogenic distillation for N-2 rejection. (C) 2015 Elsevier B.V. All rights reserved,« less

Gas-phase kinetics during diamond growth: CH4 as-growth species

NASA Astrophysics Data System (ADS)

Harris, Stephen J.

1989-04-01

We have used a one-dimensional kinetic analysis to model the gas-phase chemistry that occurred during the diamond growth experiments of Chauhan, Angus, and Gardner [J. Appl. Phys. 47, 4746 (1976)]. In those experiments the weight of diamond seed crystals heated by lamps in a CH4/H2 environment was monitored by a microbalance. No filament or electric discharge was present. Our analysis shows that diamond growth occurred in this system by direct reaction of CH4 on the diamond surface. C2H2 and CH3, which have been proposed as diamond growth species, played no significant role there, although our results do not address their possible contributions in other systems such as filament- or plasma-assisted diamond growth.

Fall season atypically warm weather event leads to substantial CH4 loss in Arctic ecosystems?

NASA Astrophysics Data System (ADS)

Zona, Donatella; Moreaux, Virginie; Liljedahl, Anna; Losacco, Salvatore; Murphy, Patrick; Oechel, Walter

2014-05-01

In the last century (during 1875-2008) high-latitudes are warming at a rate of 1.360C century-1, almost 2 times faster than the Northern Hemisphere trend (Bekryaev et al., 2010). This warming has been more intense outside of the summer season, with anomalies of 1.09, 1.59, 1.730C in the fall, winter, and spring season respectively (Bekryaev et al., 2010). This substantial temperature anomalies have the potential to increase the emission of greenhouse gas (CO2 and CH4) fluxes from arctic tundra ecosystems. In particular, CH4 emissions, which are primarily controlled by temperature (in addition to water table), can steeply increase with warming. Despite the potential relevance of CH4 emissions, very few measurements have been performed outside of the growing season across the entire Arctic, due to logistic constrains. Importantly, no flux measurements achieved a temporal and spatial data coverage sufficient to estimate with confidence an annual CH4 emissions from tundra ecosystem in Alaska, and its sensitivity to warming. Fall 2013 was unusually warm in central and northern Alaska. Following a relatively warm summer with dramatically above-average rainfall, the October mean monthly temperatures was the 4th and top warmest in Barrow (1949-2013) and Ivotuk (1998-2013), respectively. As we just upgraded several eddy covariance towers to measure CO2 and CH4 fluxes year-round, the atypical weather conditions of fall 2013 represented a unique chance for testing the sensitivity of CH4 loss to these atypically warm temperatures. All our sites across a latitudinal gradient (from the northern site, Barrow, to the southern site, Ivotuk), presented substantial CH4 loss in the fall. Importantly, in two of these sites (Barrow, Ivotuk) where the fall weather was substantially warmer than the long term trend, fall CH4 emission represented between 44-63% of the June-November cumulative emission. Surprisingly, in the southernmost site (Ivotuk), when the temperature anomaly was the

Comparison of atmospheric CH4 concentration observed by GOSAT and in-situ measurements in Thailand and India

NASA Astrophysics Data System (ADS)

Hayashida, S.; Ono, A.; Ishikawa, S.; Terao, Y.; Takeuchi, W.

2012-12-01

The concentration of atmospheric methane (CH4) has more than doubled since pre-industrial levels and the observed long-term changes in the CH4 concentration have been attributed to anthropogenic activity. However, despite the importance of atmospheric CH4 in global warming, the strength of individual sources of CH4 remains highly uncertain [e.g.,Dlugokencky et al., 2011]. To characterize and quantify the emissions of CH4 especially in Monsoon Asia and Siberia, which are the most important regions as CH4 source, we started a new project, "Characterization and Quantification of global methane emissions by utilizing GOSAT and in-situ measurements " by support of the Environment Research and Technology Development Fund (ERTDF) from June 2012 under the umbrella of Ministry of Environment Japan. The projects includes (1) satellite data applications, (2) in-situ measurements in Siberia, over Western Pacific and in Monsoon Asia, (3) development of the inverse model to derive CH4 emissions by top-down approach, and (4) flux measurements in Siberia and Asia to improve the bottom-up inventories. As an initiatory approach in the project, we started air sampling in Thailand and India where there are only a few CH4 data of direct sampling with high precision. We took eight air samples at Kohn Kaen and Pimai in Thailand on June 9 and 10, 2012. The high CH4 concentration near rice paddy field contrasted to the lower CH4 concentration near Cassava field. We are planning to take more samples in India in mid-August. The satellite CH4 data including GOSAT and SCIAMACHY are also compared with the Land Surface Water Coverage (LSWC) and the Normalized Difference Vegetation Index (NDVI). The analysis revealed the seasonal variation in of xCH4 is closely related to the variation of the LSWC, coupled with NDVI. However, the satellite measurements are all column-averaged mixing ratio (xCH4), and therefore do not necessarily reflect high CH4 concentration near the surface over the emission

BOREAS TGB-1 CH4 Concentration and Flux Data from NSA Tower Sites

NASA Technical Reports Server (NTRS)

Hall, Forrest G. (Editor); Conrad, Sara K. (Editor); Crill, Patrick; Varner, Ruth K.

2000-01-01

The BOREAS TGB-1 team made numerous measurements of trace gas concentrations and fluxes at various NSA sites. This data set contains half-hourly averages of ambient methane (CH4) measurements and calculated fluxes for the NSA-Fen in 1996 and the NSA-BP and NSA-OJP tower sites in 1994. The purpose of this study was to determine the CH4 flux from the study area by measuring ambient CH 4 concentrations. This flux can then be compared to the chamber flux measurements taken at the same sites. The data are provided in tabular ASCII files.

CO2 adsorption-assisted CH4 desorption on carbon models of coal surface: A DFT study

NASA Astrophysics Data System (ADS)

Xu, He; Chu, Wei; Huang, Xia; Sun, Wenjing; Jiang, Chengfa; Liu, Zhongqing

2016-07-01

Injection of CO2 into coal is known to improve the yields of coal-bed methane gas. However, the technology of CO2 injection-enhanced coal-bed methane (CO2-ECBM) recovery is still in its infancy with an unclear mechanism. Density functional theory (DFT) calculations were performed to elucidate the mechanism of CO2 adsorption-assisted CH4 desorption (AAD). To simulate coal surfaces, different six-ring aromatic clusters (2 × 2, 3 × 3, 4 × 4, 5 × 5, 6 × 6, and 7 × 7) were used as simplified graphene (Gr) carbon models. The adsorption and desorption of CH4 and/or CO2 on these carbon models were assessed. The results showed that a six-ring aromatic cluster model (4 × 4) can simulate the coal surface with limited approximation. The adsorption of CO2 onto these carbon models was more stable than that in the case of CH4. Further, the adsorption energies of single CH4 and CO2 in the more stable site were -15.58 and -18.16 kJ/mol, respectively. When two molecules (CO2 and CH4) interact with the surface, CO2 compels CH4 to adsorb onto the less stable site, with a resulting significant decrease in the adsorption energy of CH4 onto the surface of the carbon model with pre-adsorbed CO2. The Mulliken charges and electrostatic potentials of CH4 and CO2 adsorbed onto the surface of the carbon model were compared to determine their respective adsorption activities and changes. At the molecular level, our results showed that the adsorption of the injected CO2 promoted the desorption of CH4, the underlying mechanism of CO2-ECBM.

Effect of CH4 on the CO2 breakthrough pressure and permeability of partially saturated low-permeability sandstone in the Ordos Basin, China

NASA Astrophysics Data System (ADS)

Zhao, Yan; Yu, Qingchun

2018-01-01

The behavior of CO2 that coexists with CH4 and the effect of CH4 on the CO2 stream need to be deeply analyzed and studied, especially in the presence of water. Our previous studies investigated the breakthrough pressure and permeability of pure CO2 in five partially saturated low-permeability sandstone core samples from the Ordos Basin, and we concluded that rocks with a small pore size and low permeability show considerable sealing capacity even under unsaturated conditions. In this paper, we selected three of these samples for CO2-CH4 gas-mixture breakthrough experiments under various degrees of water saturation. The breakthrough experiments were performed by increasing the gas pressure step by step until breakthrough occurred. Then, the effluent gas mixture was collected for chromatographic partitioning analysis. The results indicate that CH4 significantly affects the breakthrough pressure and permeability of CO2. The presence of CH4 in the gas mixture increases the interfacial tension and, thus, the breakthrough pressure. Therefore, the injected gas mixture that contains the highest (lowest) mole fraction of CH4 results in the largest (smallest) breakthrough pressure. The permeability of the gas mixture is greater than that for pure CO2 because of CH4, and the effective permeability decreases with increased breakthrough pressure. Chromatographic partitioning of the effluent mixture gases indicates that CH4 breaks through ahead of CO2 as a result of its weaker solubility in water. Correlations are established between (1) the breakthrough pressure and water saturation, (2) the effective permeability and water saturation, (3) the breakthrough pressure and effective permeability, and (4) the mole fraction of CO2/CH4 in the effluent mixture gases and water saturation. These results deepen our understanding of the multi-phase flow behavior in the porous media under unsaturated conditions, which have implications for formulating emergency response plans for gas

Non-equilibrium simulation of CH4 production through the depressurization method from gas hydrate reservoirs

NASA Astrophysics Data System (ADS)

Qorbani, Khadijeh; Kvamme, Bjørn

2016-04-01

Natural gas hydrates (NGHs) in nature are formed from various hydrate formers (i.e. aqueous, gas, and adsorbed phases). As a result, due to Gibbs phase rule and the combined first and second laws of thermodynamics CH4-hydrate cannot reach thermodynamic equilibrium in real reservoir conditions. CH4 is the dominant component in NGH reservoirs. It is formed as a result of biogenic degradation of biological material in the upper few hundred meters of subsurface. It has been estimated that the amount of fuel-gas reserve in NGHs exceed the total amount of fossil fuel explored until today. Thus, these reservoirs have the potential to satisfy the energy requirements of the future. However, released CH4 from dissociated NGHs could find its way to the atmosphere and it is a far more aggressive greenhouse gas than CO2, even though its life-time is shorter. Lack of reliable field data makes it difficult to predict the production potential, as well as safety of CH4 production from NGHs. Computer simulations can be used as a tool to investigate CH4 production through different scenarios. Most hydrate simulators within academia and industry treat hydrate phase transitions as an equilibrium process and those which employ the kinetic approach utilize simple laboratory data in their models. Furthermore, it is typical to utilize a limited thermodynamic description where only temperature and pressure projections are considered. Another widely used simplification is to assume only a single route for the hydrate phase transitions. The non-equilibrium nature of hydrate indicates a need for proper kinetic models to describe hydrate dissociation and reformation in the reservoir with respect to thermodynamics variables, CH4 mole-fraction, pressure and temperature. The RetrasoCodeBright (RCB) hydrate simulator has previously been extended to model CH4-hydrate dissociation towards CH4 gas and water. CH4-hydrate is added to the RCB data-base as a pseudo mineral. Phase transitions are treated

Nitrate loading and CH4 and N2O Flux from headwater streams

NASA Astrophysics Data System (ADS)

Sousa, C. H. R. D.; Hilker, T.; Hall, F. G.; Moura, Y. M.; McAdam, E.

2014-12-01

Freshwater ecosystems transport and process significant amounts of terrestrial carbon and can be considerable sources of CO2, CH4, and N2O. A great deal of uncertainty, however, remains in both global estimates and our understanding of drivers of freshwater greenhouse gas emissions. Furthermore, small headwater streams have received insufficient attention to date and may contribute disproportionately to global GHG flux. Our objective was to quantify GHG flux and assess the impact of changes in DOC and NO3 concentrations in surface and subsurface water on flux rates in three streams in the Lamprey River watershed in New Hampshire, USA, that contrast in surface water DOC:NO3. We measured DOC, NO3 and dissolved gas concentrations in surface waters of each stream monthly from May 2011 to April 2012. Empirical measurements of reaeration coefficients were used to convert dissolved gas concentrations to fluxes. We found higher GHG concentrations and fluxes in the two streams with high DOC concentrations, particularly gases produced by anaerobic metabolism (CH4, N2O from methanogenesis and denitrification, respectively). The stream with high DOC and high NO3 showed high N2O and low CH4 flux, while the high DOC, low NO3 stream showed high CH4 and low N2O flux. Our results are consistent with a model in which C inputs drive total GHG production, while NO3 input regulates the relative importance of CH4 and N2O by suppressing methanogenesis and stimulating denitrification. The magnitude of GHG fluxes suggests that streams in this region are likely to be small sources of CO2, but potentially important sources of CH4 and N2O. Since CH4 and N2O are many times more powerful than CO2 at trapping heat in the atmosphere, freshwater emissions of these gases have the potential to offset a significant proportion of the climate benefits of the terrestrial carbon sink, a possibility that has not been sufficiently incorporated into climate models.

Nitrate loading and CH4 and N2O Flux from headwater streams

NASA Astrophysics Data System (ADS)

Schade, J. D.; Bailio, J.; McDowell, W. H.

2015-12-01

Freshwater ecosystems transport and process significant amounts of terrestrial carbon and can be considerable sources of CO2, CH4, and N2O. A great deal of uncertainty, however, remains in both global estimates and our understanding of drivers of freshwater greenhouse gas emissions. Furthermore, small headwater streams have received insufficient attention to date and may contribute disproportionately to global GHG flux. Our objective was to quantify GHG flux and assess the impact of changes in DOC and NO3 concentrations in surface and subsurface water on flux rates in three streams in the Lamprey River watershed in New Hampshire, USA, that contrast in surface water DOC:NO3. We measured DOC, NO3 and dissolved gas concentrations in surface waters of each stream monthly from May 2011 to April 2012. Empirical measurements of reaeration coefficients were used to convert dissolved gas concentrations to fluxes. We found higher GHG concentrations and fluxes in the two streams with high DOC concentrations, particularly gases produced by anaerobic metabolism (CH4, N2O from methanogenesis and denitrification, respectively). The stream with high DOC and high NO3 showed high N2O and low CH4 flux, while the high DOC, low NO3 stream showed high CH4 and low N2O flux. Our results are consistent with a model in which C inputs drive total GHG production, while NO3 input regulates the relative importance of CH4 and N2O by suppressing methanogenesis and stimulating denitrification. The magnitude of GHG fluxes suggests that streams in this region are likely to be small sources of CO2, but potentially important sources of CH4 and N2O. Since CH4 and N2O are many times more powerful than CO2 at trapping heat in the atmosphere, freshwater emissions of these gases have the potential to offset a significant proportion of the climate benefits of the terrestrial carbon sink, a possibility that has not been sufficiently incorporated into climate models.

Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.

Volcanism and post-magmatism contribute significant annual methane (CH 4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH 4 (as well as carbon dioxide (CO 2) and other gases), but the ultimate sources of this CH 4 flux have not been elucidated. In this paper, we use dual stable isotope analysis (δ 2H and δ 13C) of CH 4 sampled from ten high-temperature geothermalmore » pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ 13C and δ 2H values of CH 4 emitted from hot springs ( 26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ 13C CH4 and δ 13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH 4, or with equilibration of CH 4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ 13C CH4 and δ 13C CO2 ranged from ~ 250–350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ 2H H2O of the thermal springs and the measured δ 2H CH4 values are consistent with equilibration between the source water and the CH 4 at the formation temperatures. Though the ultimate origin of the CH 4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C 1/C 2+ composition of the gases is more consistent with abiotic origins for most of the samples. Finally, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH 4 flux from the Yellowstone National Park volcanic system.« less

Dual stable isotopes of CH 4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO 2

DOE PAGES

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.; ...

2017-05-16

Volcanism and post-magmatism contribute significant annual methane (CH 4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH 4 (as well as carbon dioxide (CO 2) and other gases), but the ultimate sources of this CH 4 flux have not been elucidated. In this paper, we use dual stable isotope analysis (δ 2H and δ 13C) of CH 4 sampled from ten high-temperature geothermalmore » pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ 13C and δ 2H values of CH 4 emitted from hot springs ( 26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ 13C CH4 and δ 13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH 4, or with equilibration of CH 4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ 13C CH4 and δ 13C CO2 ranged from ~ 250–350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ 2H H2O of the thermal springs and the measured δ 2H CH4 values are consistent with equilibration between the source water and the CH 4 at the formation temperatures. Though the ultimate origin of the CH 4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C 1/C 2+ composition of the gases is more consistent with abiotic origins for most of the samples. Finally, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH 4 flux from the Yellowstone National Park volcanic system.« less

Background CH4 and N2O fluxes in low-input short rotation coppice

NASA Astrophysics Data System (ADS)

Görres, Carolyn-Monika; Zenone, Terenzio; Ceulemans, Reinhart

2016-04-01

Extensively managed short rotation coppice systems are characterized by low fluxes of CH4 and N2O. However due to the large global warming potential of these trace gases (GWP100: CH4: 34, N2O: 298), such background fluxes can still significantly contribute to offsetting the CO2 uptake of short rotation coppice systems. Recent technological advances in fast-response CH4 and N2O analysers have improved our capability to capture these background fluxes, but their quantification still remains a challenge. As an example, we present here CH4 and N2O fluxes from a short-rotation bioenergy plantation in Belgium. Poplars have been planted in a double-row system on a loamy sand in 2010 and coppiced in the beginning of 2012 and 2014 (two-year rotation system). In 2013 (June - November) and 2014 (April - August), the plantation's CH4 and N2O fluxes were measured in parallel with an eddy covariance tower (EC) and an automated chamber system (AC). The EC had a detection limit of 13.68 and 0.76 μmol m-2 h-1 for CH4 and N2O, respectively. The median detection limit of the AC was 0.38 and 0.08 μmol m-2 h-1 for CH4 and N2O, respectively. The EC picked up a few high CH4 emission events with daily averages >100 μmol m-2 h-1, but a large proportion of the measured fluxes were within the EC's detection limit. The same was true for the EC-derived N2O fluxes where the daily average flux was often close to the detection limit. Sporadically, some negative (uptake) fluxes of N2O were observed. On the basis of the EC data, no clear link was found between CH4 and N2O fluxes and environmental variables. The problem with fluxes within the EC detection limit is that a significant amount of the values can show the opposite sign, thus "mirroring" the true flux. Subsequently, environmental controls of background trace gas fluxes might be disguised in the analysis. As a next step, it will be tested if potential environmental drivers of background CH4 and N2O fluxes at the plantation can be

An eight-dimensional quantum dynamics study of the Cl + CH{sub 4}→ HCl + CH{sub 3} reaction

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Na; Yang, Minghui, E-mail: yangmh@wipm.ac.cn

2015-10-07

In this work, the later-barrier reaction Cl + CH{sub 4} → HCl + CH{sub 3} is investigated with an eight-dimensional quantum dynamics method [R. Liu et al., J. Chem. Phys. 137, 174113 (2012)] on the ab initio potential energy surface of Czakó and Bowman [J. Chem. Phys. 136, 044307 (2012)]. The reaction probabilities with CH{sub 4} initially in its ground and vibrationally excited states are calculated with a time-dependent wavepacket method. The theoretical integral cross sections (ICSs) are extensively compared with the available experimental measurements. For the ground state reaction, the theoretical ICSs excellently agree with the experimental ones. Themore » good agreements are also achieved for ratios between ICSs of excited reactions. For ICS ratios between various states, the theoretical values are also consistent with the experimental observations. The rate constants over 200-2000 K are calculated and the non-Arrhenius effect has been observed which is coincident with the previous experimental observations and theoretical calculations.« less

Kinetic conversion of CO to CH4 in the Solar System

NASA Technical Reports Server (NTRS)

Yung, Y. L.; Allen, M.; Pinto, J. P.

1991-01-01

Some of the most interesting chemistry in the Solar System involves changes in the oxidation state of the simple carbon species. The chemical pathways for the conversion of CH4 to CO and CO2 are for the most part known. The reverse process, the reduction of CO to CH4, is, however, poorly understood. This is surprising in view of the importance of the reduction process in the chemistry of the Solar System. Recently we investigated the chemical kinetics of a hitherto unsuspected reaction. It is argued that the formation of the methoxy radical (CH3O) from H+H2CO may play an essential role in the reduction of CO to CH4. The rate coefficient for this reaction has been estimated using the approximate theory of J. Troe and transition state theory. We will discuss the implications of this reaction for the chemistry of CO on Jupiter, in the solar nebula, for interpreting the laboratory experiments of A. Bar-Nun and A. Shaviv and A. Bar-Nun and S. Chang, and for organic synthesis in the prebiotic terrestrial atmosphere. The possible relation of CO reduction in the solar nebula and polyoxymethylene observed in comet Halley will be discussed.

Resolved 12CH2D2 and 13CH3D in CH4 as Sensitive Indicators of Disequilibrium and Equilibrium during Microbial Methane Cycling

NASA Astrophysics Data System (ADS)

Ash, J. L.; Egger, M.; Slomp, C. P.; Kohl, I. E.; Treude, T.; Rumble, D.; Young, E. D.

2016-12-01

The ability to measure the relative concentrations of at least two doubly-substituted rare isotopologues of gases with biogeochemical relevance provides new constraints on sources and sinks of these gases. In particular, as shown recently for O2, the use of two independent, rare isotopologues allows for detection of thermodynamic intra-species equilibrium and disequilibrium. Here, we report the first measurements of fully resolved 13CH3D and 12CH2D2 from natural samples of microbial methane gas. A suite of sedimentary methane samples from the Bornholm Basin in the Baltic Sea was collected during IODP Exp. 347. Sample depths range from 2-20 meters below seafloor (mbsf). Methane concentrations decrease with depth, and mcrA (a marker for methanogenesis and methanotropy) is present throughout. See Figure. Both Δ13CH3D and Δ12CH2D2 increase with depth as methane concentrations decrease with the shallowest samples exhibiting disequilibrium by up to 2‰ in Δ13CH3D and 13‰ in Δ12CH2D2 while the deepest samples approach isotopic thermodynamic equilibrium (marked by grey bars in Figure). The Fe-mediated anaerobic oxidation of methane (Fe-AOM) has been inferred in these sediments by geochemical modeling . Slow methane cycling by methanogensis and methanotrophy is likely responsible for the approach to isotopic bond order equilibrium in CH4 with depth, consistent with Fe-AOM. While axenic culturing experiments generate methane with large deficits in 12CH2D2 (reported at this meeting), these data from the Baltic Sea demonstrate that isotopic equilibrium can be achieved during microbial recycling of methane. In the absence of Δ12CH2D2, the Δ13CH3D values alone could be misinterpreted as representing gradients in temperature due perhaps to exothermic organic matter degradation. The combination of both mass-18 rare isotopologues of methane provides the means to distinguish equilibrium from disequilibrium and probe microbial methane cycling even where Δ13CH3D suggests

Nutrient load can lead to enhanced CH4 fluxes through changes in vegetation, peat surface elevation and water table depth in ombrotrophic bog

NASA Astrophysics Data System (ADS)

Juutinen, Sari; Bubier, Jill; Larmola, Tuula; Humphreys, Elyn; Arnkil, Sini; Roy, Cameron; Moore, Tim

2016-04-01

Atmospheric nitrogen (N) deposition has led to nutrient enrichment in wetlands, particularly in temperate areas, affecting plant community composition, carbon (C) cycling, and microbial dynamics. It is vital to understand the temporal scales and mechanisms of the changes, because peatlands are long-term sinks of C, but sources of methane (CH4), an important greenhouse gas. Rainwater fed (ombrotrophic) bogs are considered to be vulnerable to nutrient loading due to their natural nutrient poor status. We fertilized Mer Bleue Bog, a Sphagnum moss and evergreen shrub-dominated ombrotrophic bog near Ottawa, Ontario, now for 11-16 years with N (NO3 NH4) at 0.6, 3.2, and 6.4 g N m-2 y-1 (~5, 10 and 20 times ambient N deposition during summer months) with and without phosphorus (P) and potassium (K). Treatments were applied to triplicate plots (3 x 3 m) from May - August 2000-2015 and control plots received distilled water. We measured CH4 fluxes with static chambers weekly from May to September 2015 and peat samples were incubated in laboratory to measure CH4 production and consumption potentials. Methane fluxes at the site were generally low, but after 16 years, mean CH4 emissions have increased and more than doubled in high nitrogen addition treatments if P and K input was also increased (3.2 and 6.4 g N m-2yr-1 with PK), owing to drastic changes in vegetation and soil moisture. Vegetation changes include a loss of Sphagnum moss and introduction of new species, typical to minerogenic mires, which together with increased decomposition have led to decreased surface elevation and to higher water table level relative to the surface. The trajectories indicate that the N only treatments may result in similar responses, but only over longer time scales. Elevated atmospheric deposition of nutrients to peatlands may increase loss of C not only due to changes in CO2 exchange but also due to enhanced CH4 emissions in peatlands through a complex suite of feedbacks and interactions

CO2 and CH4 exchange by Phragmites australis under different climates

NASA Astrophysics Data System (ADS)

Serrano Ortiz, Penélope; Chojnickic, Bogdan H.; Sánchez-Cañete, Enrique P.; Kowalska, Natalia; López-Ballesteros, Ana; Fernández, Néstor; Urbaniak, Marek; Olejnik, Janusz; Kowalski, Andrew S.

2015-04-01

The key role of wetlands regarding global warming is the resulting balance between net CO2 assimilation, via photosynthesis, and CO2 and CH4 emissions, given the potential to release stored carbon, because of the high temperature sensitivity of heterotrophic soil respiration and anoxic conditions. However, it is still unknown whether wetlands will convert from long-term carbon sinks to sources as a result of climate change and other anthropogenic effects such as land use changes. Phragmites australis is one of the most common species found in wetlands and is considered the most globally widespread and productive plant species in this type of ecosystem. In this context, the main objective of this study is to analyse the GHG exchange (CO2 and CH4) of two wetlands with Phragmites australis as the dominant species under different climates using the eddy covariance (EC) technique. The first site, Padul, is located in southern Spain, with a sub-humid warm climate, characterised by a mean annual temperature of 16°C and annual precipitation of ca. 470 mm, with a very dry summer. The second site, Rzecin is located in Poland with a mean annual temperature of 8°C, and annual precipitation around 600mm with no dry season. The Padul EC station is equipped with two infrared gas analysers to measure CO2 and CH4 fluxes (LI-7200 and LI-7700 respectively) while the Rzecin EC station has the same CH4 sensor as Padul, but also a sensor measuring both GHG fluxes (DLT-100 Fast Methane Analyser, Los Gatos). In this study, we present: i) the results of a CH4 analyser inter-comparison campaign (LI-7700 vs. Los Gatos), ii) a comparative analysis of the functional behaviour of respiration and photosynthesis in both sites testing relationships between CO2 fluxes measured with the EC technique and meteorological variables such as temperature and direct or diffuse radiation and iii) the CH4 dynamicsat both sites by identifying, when possible, annual, seasonal and diurnal patterns.

Environmental factors controlling methane emissions from peatlands in northern Minnesota

NASA Technical Reports Server (NTRS)

Dise, Nancy B.; Gorham, Eville; Verry, Elon S.

1993-01-01

The environmental factors affecting the emission of methane from peatlands were investigated by correlating CH4 emission data for two years, obtained from five different peatland ecosystems in northern Minnesota, with peat temperature, water table position, and degree of peat humification. The relationship obtained between the CH4 flux and these factors was compared to results from a field manipulation experiment in which the water table was artificially raised in three experimental plots within the driest peatland. It was found that peat temperature, water table position, and degree of peat humification explained 91 percent of the variance in log CH4 flux, successfully predicted annual CH4 emission from individual wetlands, and predicted the change in flux due to the water table manipulation. Raising the water table in the bog corrals by an average of 6 cm in autumn 1989 and 10 cm in summer 1990 increased CH4 emission by 2.5 and 2.2 times, respectively.

The spectroscopic observation of the CH radical in its a4Sigma(-) state

NASA Technical Reports Server (NTRS)

Nelis, Thomas; Brown, John M.; Evenson, Kenneth M.

1988-01-01

The first spectroscopic observation of CH in the a 4Sigma(0-) state are reported. The molecule was generated in a discharge-flow system in the reaction betweeen fluorine atoms and methane or between oxygen atoms and acetylene at a total pressure of about 1 Torr. Several resonances associated with the N = 1 - 0 transitions of 4Sigma(-) CH were observed at three separate laser wavelengths, while those for the N = 2 - 1 transition were observed at two wavelengths. Each observed Zeeman component consists of a well-split doublet arising from proton hyperfine structure. The reasons for assigning the observations to CH in its a 4Sigma(-) state are discussed.

The relationships between termite mound CH4/CO2 emissions and internal concentration ratios are species specific

NASA Astrophysics Data System (ADS)

Jamali, H.; Livesley, S. J.; Hutley, L. B.; Fest, B.; Arndt, S. K.

2013-04-01

We investigated the relative importance of CH4 and CO2 fluxes from soil and termite mounds at four different sites in the tropical savannas of northern Australia near Darwin and assessed different methods to indirectly predict CH4 fluxes based on CO2 fluxes and internal gas concentrations. The annual flux from termite mounds and surrounding soil was dominated by CO2 with large variations among sites. On a carbon dioxide equivalent (CO2-e) basis, annual CH4 flux estimates from termite mounds were 5- to 46-fold smaller than the concurrent annual CO2 flux estimates. Differences between annual soil CO2 and soil CH4 (CO2-e) fluxes were even greater, soil CO2 fluxes being almost three orders of magnitude greater than soil CH4 (CO2-e) fluxes at site. The contribution of CH4 and CO2 emissions from termite mounds to the total CH4 and CO2 emissions from termite mounds and soil in CO2-e was less than 1%. There were significant relationships between mound CH4 flux and mound CO2 flux, enabling the prediction of CH4 flux from measured CO2 flux; however, these relationships were clearly termite species specific. We also observed significant relationships between mound flux and gas concentration inside mound, for both CH4 and CO2, and for all termite species, thereby enabling the prediction of flux from measured mound internal gas concentration. However, these relationships were also termite species specific. Using the relationship between mound internal gas concentration and flux from one species to predict mound fluxes from other termite species (as has been done in the past) would result in errors of more than 5-fold for mound CH4 flux and 3-fold for mound CO2 flux. This study highlights that CO2 fluxes from termite mounds are generally more than one order of magnitude greater than CH4 fluxes. There are species-specific relationships between CH4 and CO2 fluxes from a mound, and between the inside mound concentration of a gas and the mound flux emission of the same gas, but

The Arctic CH4 sink and its implications for the permafrost carbon feedbacks to the global climate system

NASA Astrophysics Data System (ADS)

Juncher Jørgensen, Christian; Christiansen, Jesper; Mariager, Tue; Hugelius, Gustaf

2016-04-01

Using atmospheric methane (CH4), certain soil microbes are able to sustain their metabolism, and in turn remove this powerful greenhouse gas from the atmosphere. While the process of CH4 oxidation is a common feature in most natural and unmanaged ecosystems in temperate and boreal ecosystems, the interactions between soil physical properties and abiotic process drivers, net landscape exchange and spatial patterns across Arctic drylands remains highly uncertain. Recent works show consistent CH4 comsumption in upland dry tundra soils in Arctic and High Arctic environments (Christiansen et al., 2014, Biogeochemistry 122; Jørgensen et al., 2015, Nature Geoscience 8; Lau et al., 2015, The ISME Journal 9). In these dominantly dry or barren soil ecosystems, CH4 consumption has been observed to significantly exceed the amounts of CH4 emitted from adjacent wetlands. These observations point to a potentially important but largely overlooked component of the global soil-climate system interaction and a counterperspective to the conceptual understanding of the Arctic being a only a source of CH4. However, due to our limited knowledge of spatiotemporal occurrence of CH4 consumption across a wider range of the Arctic landscape we are left with substantial uncertainites and an overall unconstrained range estimate of this terrestrial CH4 sink and its potential effects on permafrost carbon feedback to the atmospheric CH4 concentration. To address this important knowledge gap and identify the most relevant spatial scaling parameters, we studied in situ CH4 net exchange across a large landscape transect on West Greenland. The transect representated soils formed from the dominant geological parent materials of dry upland tundra soils found in the ice-free land areas of Western Greenland, i.e. 1) granitic/gneissic parent material, 2) basaltic parent material and 3) sedimentary deposits. Results show that the dynamic variations in soil physical properties and soil hydrology exerts an

Activation of CH4 by Th(+) as studied by guided ion beam mass spectrometry and quantum chemistry.

PubMed

Cox, Richard M; Armentrout, P B; de Jong, Wibe A

2015-04-06

The reaction of atomic thorium cations with CH4 (CD4) and the collision-induced dissociation (CID) of ThCH4(+) with Xe are studied using guided ion beam tandem mass spectrometry. In the methane reactions at low energies, ThCH2(+) (ThCD2(+)) is the only product; however, the energy dependence of the cross-section is inconsistent with a barrierless exothermic reaction as previously assumed on the basis of ion cyclotron resonance mass spectrometry results. The dominant product at higher energies is ThH(+) (ThD(+)), with ThCH3(+) (ThCD3(+)) having a similar threshold energy. The latter product subsequently decomposes at still higher energies to ThCH(+) (ThCD(+)). CID of ThCH4(+) yields atomic Th(+) as the exclusive product. The cross-sections of all product ions are modeled to provide 0 K bond dissociation energies (in eV) of D0(Th(+)-H) ≥ 2.25 ± 0.18, D0(Th(+)-CH) = 6.19 ± 0.16, D0(Th(+)-CH2) ≥ 4.54 ± 0.09, D0(Th(+)-CH3) = 2.60 ± 0.30, and D0(Th(+)-CH4) = 0.47 ± 0.05. Quantum chemical calculations at several levels of theory are used to explore the potential energy surfaces for activation of methane by Th(+), and the effects of spin-orbit coupling are carefully considered. When spin-orbit coupling is explicitly considered, a barrier for C-H bond activation that is consistent with the threshold measured for ThCH2(+) formation (0.17 ± 0.02 eV) is found at all levels of theory, whereas this barrier is observed only at the BHLYP and CCSD(T) levels otherwise. The observation that the CID of the ThCH4(+) complex produces Th(+) as the only product with a threshold of 0.47 eV indicates that this species has a Th(+)(CH4) structure, which is also consistent with a barrier for C-H bond activation. This barrier is thought to exist as a result of the mixed ((4)F,(2)D) electronic character of the Th(+) J = (3)/2 ground level combined with extensive spin-orbit effects.

Further development of a global pollution model for CO, CH4, and CH2 O

NASA Technical Reports Server (NTRS)

Peters, L. K.

1975-01-01

Global tropospheric pollution models are developed that describe the transport and the physical and chemical processes occurring between the principal sources and sinks of CH4 and CO. Results are given of long term static chemical kinetic computer simulations and preliminary short term dynamic simulations.

Kinetic and theoretical studies on the protonation of [Ni(2-SC6H4N){PhP(CH2CH2PPh2)2}]+: nitrogen versus sulfur as the protonation site.

PubMed

Petrou, Athinoula L; Koutselos, Andreas D; Wahab, Hilal S; Clegg, William; Harrington, Ross W; Henderson, Richard A

2011-02-07

The complexes [Ni(4-Spy)(triphos)]BPh(4) and [Ni(2-Spy)(triphos)]BPh(4) {triphos = PhP(CH(2)CH(2)PPh(2))(2), 4-Spy = 4-pyridinethiolate, 2-Spy = 2-pyridinethiolate} have been prepared and characterized both spectroscopically and using X-ray crystallography. In both complexes the triphos is a tridentate ligand. However, [Ni(4-Spy)(triphos)](+) comprises a 4-coordinate, square-planar nickel with the 4-Spy ligand bound to the nickel through the sulfur while [Ni(2-Spy)(triphos)](+) contains a 5-coordinate, trigonal-bipyramidal nickel with a bidentate 2-Spy ligand bound to the nickel through both sulfur and nitrogen. The kinetics of the reactions of [Ni(4-Spy)(triphos)](+) and [Ni(2-Spy)(triphos)](+) with lutH(+) (lut = 2,6-dimethylpyridine) in MeCN have been studied using stopped-flow spectrophotometry, and the two complexes show very different reactivities. The reaction of [Ni(4-Spy)(triphos)](+) with lutH(+) is complete within the deadtime of the stopped-flow apparatus (2 ms) and corresponds to protonation of the nitrogen. However, upon mixing [Ni(2-Spy)(triphos)](+) and lutH(+) a reaction is observed (on the seconds time scale) to produce an equilibrium mixture. The mechanistic interpretation of the rate law has been aided by the application of MSINDO semiempirical and ADF calculations. The kinetics and calculations are consistent with the reaction between [Ni(2-Spy)(triphos)](+) and lutH(+) involving initial protonation of the sulfur followed by dissociation of the nitrogen and subsequent transfer of the proton from sulfur to nitrogen. The factors affecting the position of protonation and the coupling of the coordination state of the 2-pyridinethiolate ligand to the site of protonation are discussed.

F -state quenching with CH 4 for buffer-gas cooled 171 Y b + frequency standard [Methane (CH4) for quenching the F-state in trapped Yb+ ions].

DOE PAGES

Jau, Y. -Y.; Hunker, J. D.; Schwindt, P. D. D.

2015-11-01

We report that methane, CH 4, can be used as an efficient F-state quenching gas for trapped ytterbium ions. The quenching rate coefficient is measured to be (2.8 ± 0.3) × 10 6 s -1 Torr -1. For applications that use microwave hyperfine transitions of the ground-state 171Y b ions, the CH4 induced frequency shift coefficient and the decoherence rate coefficient are measured as δν/ν = (-3.6 ± 0.1) × 10 -6 Torr -1 and 1/T2 = (1.5 ± 0.2) × 10 5 s -1 Torr -1. In our buffer-gas cooled 171Y b+ microwave clock system, we find that onlymore » ≤10 -8 Torr of CH 4 is required under normal operating conditions to efficiently clear the F-state and maintain ≥85% of trapped ions in the ground state with insignificant pressure shift and collisional decoherence of the clock resonance.« less

Stable isotope ratios of atmospheric CO_{2} and CH_{4} over Siberia measured at ZOTTO

NASA Astrophysics Data System (ADS)

Timokhina, Anastasiya; Prokushkin, Anatily; Lavric, Jost; Heimann, Martin

2016-04-01

The boreal and arctic zones of Siberia housing the large amounts of carbon stored in the living biomass of forests and wetlands, as well as in soils and specifically permafrost, play a crucial role in earth's global carbon cycle. The long-term studies of greenhouse gases (GHG) concentrations are important instruments to analyze the response of these systems to climate warming. In parallel to GHG observations, the measurements of their stable isotopic composition can provide useful information for distinguishing contribution of individual GHG source to their atmospheric variations, since each source has its own isotopic signature. In this study we report first results of laboratory analyses of the CO2 and CH4 concentrations, the stable isotope ratio of δ13C-CO2, δ18O-CO2, δ13C-CH4, δD-CH4 measured in one-liter glass flasks which were obtained from 301 height of ZOTTO (Zotino Tall Tower Observatory, near 60° N, 90° E, about 20 km west of the Yenisei River) during 2008 - 2013 and 2010 - 2013 for stable isotope composition of CO2 and CH4. The magnitudes of δ13C-CO2 and δ18O-CO2 in a seasonal cycle are -1.4±0.1‰ (-7.6 - -9.0‰) and -2.2±0.2‰ (-0.1 - -2.3‰), respectively. The δ13C-CO2 seasonal pattern opposes the CO2 concentrations, with a gradual enrichment in heavy isotope occurring during May - July, reflecting its discrimination in photosynthesis, and further depletion in August - September as photosynthetic activity decreases comparatively to ecosystem respiration. Relationship between the CO2 concentrations and respective δ13C-CO2 (Keeling plot) reveals isotopic source signature for growing season (May - September) -27.3±1.4‰ and -30.4±2.5‰ for winter (January - March). The behavior of δ18O-CO2 associated with both high photosynthetic rate in the June (enrichment of atmospheric CO2 by 18O as consequence of CO2 equilibrium with "heavy" leaf water) and respiratory activity of forest floor in June - October (depletion of respired CO2 by 18O

The composition of Saturn's atmosphere at northern temperate latitudes from Voyager IRIS spectra - NH3, PH3, C2H2, C2H6, CH3D, CH4, and the Saturnian D/H isotopic ratio

NASA Technical Reports Server (NTRS)

Courtin, R.; Gautier, D.; Marten, A.; Bezard, B.; Hanel, R.

1984-01-01

The vertical distributions and mixing ratios of minor constituents in the northern hemisphere of Saturn are investigated. Results are obtained for NH3, PH3, C2H2, C2H6, CH3D, and CH4; the D/H ratio is obtained from the CH4 and CH3D abundances. The NH3 mixing ratio in the upper atmosphere is found to be compatible with the saturated partial pressure. The inferred PH3/H2 ratio of 1.4 + or - 0.8 x 10 to the -6th is higher than the value derived from the solar P/H ratio. The stratospheric C2H2/H2 and C2H6/H2 ratios are, respectively, 2.1 + or - 1.4 x 10 to the -7th and 3.0 + or - 1.1 x 10 to the -6th; the latter decreases sharply below the 20-50 mbar level. The results for CH3D/H2 and CH4/H2 imply an enrichment of Saturn's upper atmosphere in carbon by a factor of at least three over the solar abundance. The interpretation of two NH3 lines in the five-micron window suggests a NH3/H2 ratio at the two bar level below the solar value.

Crystal and molecular structure of the first dibino non-geminal macrocyclic dicyclophosphazene, & {;N 3P 3Cl 4[HN(CH 2) 3O(CH 2) 2O(CH 2) 3NH]&}; 2

NASA Astrophysics Data System (ADS)

Enjalbert, Renée; Galy, Jean; Sournies, François; Labarre, Jean-François

1990-04-01

Reaction of N 3P 3Cl 6 with the 4,7-dioxadecane-1,10-diamine (coded as 3O2O3) using an Et 2O/Na 2CO 3 water interface process leads to the DIBINO non-geminal 30-membered macrocyclic dicyclophosphazene &{;N 3P 3Cl 4[HN(CH 2) 3O(CH 2) 2O(CH 2) 3NH]&}; 2. This 30-crown-ether-like architecture crystallizes in the triclinic system, P1, a=9.019(6), b=9.224(5), c=11.542(8) Å, α=94.87(4), β=95.97(4), γ=99.68(3)°, V=936(1) Å 3, Dx=1.599 Mg m -3, R=0.049 for 2862 unique reflections and 199 variable parameters. The structure exhibits a spatial arrangement of two N 3P 3Cl 4 with two [HN(CH 2) 3O(CH 2) 3O(CH 2) 3NH] as bridges on different P atoms of N 3P 3 rings. Moreover, the two N 3P 3 rings are trans to the average plane of the 30-membered macrocycle ("chair" conformation).

Assessing the British Isles CH4 flux using aircraft and ground-based sampling: a case study on 12 May 2015

NASA Astrophysics Data System (ADS)

Pitt, Joseph

2017-04-01

Aircraft and ground-based sampling of atmospheric greenhouse gas composition over the British Isles was conducted between 2014 and 2016 as part of the Greenhouse gAs UK and Global Emissions (GAUGE) project. We report a case study focussing on two research aircraft flights conducted on 12 May 2015 to sample inflow and outflow across the British Isles. We have employed the NAME Lagrangian dispersion model to simulate CH4 mole fraction enhancements corresponding to aircraft and ground-based sample times and locations, using CH4 surface fluxes derived from a composite flux inventory, which included both anthropogenic and natural sources. For each sampling location, variations in the baseline CH4 mole fraction were derived using the MOZART global chemical transport model, and added to the NAME enhancements to produce a dataset of modelled CH4 mole fractions which can be compared to the measurements. Using a multiple variable regression technique, we derive CH4 fluxes for the British Isles region from both aircraft and ground-based datasets. We discuss the applicability of our approach for both datasets, and conclude that in this case the assumptions inherent in our method are much better satisfied for the aircraft data than for the ground-based data. Using the aircraft data we derive a possible range of scale factors for the prior inventory flux of 0.53 - 0.97, with a central estimate of 0.82 based on our assessment of the most likely apportionment of model uncertainty. This leads to a posterior estimate of the British Isles CH4 flux of 67 kg s-1 - 121 kg s-1, with a central value of 103 kg s-1.

[Methane fluxes and controlling factors in the intertidal zone of the Yellow River estuary in autumn].

PubMed

Jiang, Huan-Huan; Sun, Zhi-Gao; Wang, Ling-Ling; Mou, Xiao-Jie; Sun, Wan-Long; Song, Hong-Li; Sun, Wen-Guang

2012-02-01

The characteristics of methane (CH4) fluxes from tidal wetlands of the Yellow River estuary were observed in situ with static-chamber and GC methods in September and October 2009, and the key factors affecting CH4 fluxes were discussed. From the aspect of space, the CH4 flux ranges in high tidal wetland, middle tidal wetland, low tidal wetland, bare flat are - 0.206-1.264, -0.197-0.431, -0.125-0.659 and -0.742-1.767 mg x (m2 x h)(-1), the day average fluxes are 0.089, 0.038, 0.197 and 0.169 mg x (m2 x h)(-1), respectively, indicating that the tidal wetlands are the sources of CH4 and the source function of CH4 differed among the four study sites, in the order of low tidal wetland > bare flat > high tidal wetland > middle tidal wetland. From the aspect of time, the ranges of CH4 fluxes from the tidal wetland ecosystems are -0.444-1.767 and - 0.742- 1.264 mg x (m2 x h)(-1), and the day average fluxes are 0.218 and 0.028 mg x (m2 x h)(-1) in September and October, respectively. The CH4 fluxes in each tidal wetland in September are higher than those in October except that the high tidal wetland acts as weak sink in September. Further studies indicate that the changes of environmental factors in the Yellow River estuary are complicated, and the CH4 fluxes are affected by multiple factors. The differences of CH4 fluxes characteristics among different tidal wetlands in autumn are probably related to temperature (especially atmospheric temperature) and vegetation growth status, while the effects of water or salinity condition and tide status on the CH4 flux characteristics might not be ignored.

CH4 dissociation in the early stage of graphene growth on Fe-Cu(100) surface: Theoretical insights

NASA Astrophysics Data System (ADS)

Tian, Baoyang; Liu, Tianhui; Yang, YanYan; Li, Kai; Wu, Zhijian; Wang, Ying

2018-01-01

The mechanism of CH4 dissociation and carbon nucleation process on the Fe doped Cu(100) surface were investigated systematically by using the density functional theory (DFT) calculations and microkinetic model. The activity of the Cu(100) surface was improved by the doped Fe atom and the atomic Fe on the Fe-Cu(100) surface was the reaction center due to the synergistic effect. In the dissociation process of CH4, CH3 → CH2 + H was regarded as the rate-determining step. The results obtained from the microkinetic model showed that the coverage of CHx(x = 1-3) was gradually decreased with the temperature increasing and CH3 was always the major intermediate at the broad range of the temperature (from 1035 to 1080 °C) and the ratio of H2/CH4 (from 0 to 5). It is also found that the reaction rates were increased with the temperature increasing. However, the reaction rates were reduced (or increased) at the range of H2/CH4 = 0-0.2 (or H2/CH4 > 0.2). It is noted that controlling the H2 partial pressure was an effective method to regulate the major intermediates and reaction rates of CH4 dissociation and further influence the growing process of graphene.

Field-scale simulation of methane emissions from coastal wetlands in China using an improved version of CH4MODwetland.

PubMed

Li, Tingting; Xie, Baohua; Wang, Guocheng; Zhang, Wen; Zhang, Qing; Vesala, Timo; Raivonen, Maarit

2016-07-15

Coastal wetlands are important CH4 sources to the atmosphere. Coastal wetlands account for ~10% of the total area of natural wetlands in China, but the size of this potential CH4 source remains highly uncertain. We introduced the influence of salinity on CH4 production and CH4 diffusion into a biogeophysical model named CH4MODwetland so that it can be used in coastal wetlands. The improved model can generally simulate seasonal CH4 variations from tidal marshes dominated by Phragmites and Scirpus. However, the model underestimated winter CH4 fluxes from tidal marshes in the Yellow River Delta and YanCheng Estuary. It also failed to capture the accurate timing of the CH4 peaks in YanCheng Estuary and ChongMing Island in 2012. The improved model could generally simulate the difference between the annual mean CH4 fluxes from mangrove sites in GuangZhou and HaiKou city under different salinity and water table depth conditions, although fluxes were systematically underestimated in the mangrove site of HaiKou city. Using the improved model, the seasonal CH4 emissions simulated across all of the coastal wetlands ranged from 0.1 to 44.90gm(-2), with an average value of 7.89gm(-2), which is in good agreement with the observed values. The improved model significantly decreased the RMSE and RMD from 424% to 14% and 314% to -2%, respectively, and improved the EF from -18.30 to 0.99. Model sensitivity analysis showed that CH4 emissions were most sensitive to Pox in the tidal marshes and salinity in the mangroves. The results show that previous studies may have overestimated CH4 emissions on a regional or global scale by neglecting the influence of salinity. In general, the CH4MODwetland model can simulate seasonal CH4 emissions from different types of coastal wetlands under various conditions. Further improvements of CH4MODwetland should include the specific characteristics of CH4 processes in mangroves to decrease the uncertainty in estimating regional or global CH4 emissions

Ionization yields, total absorption, and dissociative photoionization cross sections of CH4 from 110-950 A

NASA Technical Reports Server (NTRS)

Samson, James A. R.; Haddad, G. N.; Masuoka, T.; Pareek, P. N.; Kilcoyne, D. A. L.

1989-01-01

Absolute absorption and photoionization cross sections of methane have been measured with an accuracy of about 2 or 3 percent over most of the wavelength range from 950 to 110 A. Also, dissociative photoionization cross sections were measured for the production of CH4(+), CH3(+), CH2(+), CH(+), and C(+) from their respective thresholds to 159 A, and for H(+) and H2(+) measurements were made down to 240 A. Fragmentation was observed at all excited ionic states of CH4.

The relationship between termite mound CH4/CO2 emissions and internal concentration ratios are species specific

NASA Astrophysics Data System (ADS)

Jamali, H.; Livesley, S. J.; Hutley, L. B.; Fest, B.; Arndt, S. K.

2012-12-01

1. We investigated the relative importance of CH4 and CO2 fluxes from soil and termite mounds at four different sites in the tropical savannas of Northern Australia near Darwin and assessed different methods to indirectly predict CH4 fluxes based on CO2 fluxes and internal gas concentrations. 2. The annual flux from termite mounds and surrounding soil was dominated by CO2 with large variations among sites. On a CO2-e basis, annual CH4 flux estimates from termite mounds were 5- to 46-fold smaller than the concurrent annual CO2 flux estimates. Differences between annual soil CO2 and soil CH4 (CO2-e) fluxes were even greater, soil CO2 fluxes being almost three orders of magnitude greater than soil CH4 (CO2-e) fluxes at site. 3. There were significant relationships between mound CH4 flux and mound CO2 flux, enabling the prediction of CH4 flux from measured CO2 flux, however, these relationships were clearly termite species specific. 4. We also observed significant relationships between mound flux and gas concentration inside mound, for both CH4 and CO2, and for all termite species, thereby enabling the prediction of flux from measured mound internal gas concentration. However, these relationships were also termite species specific. Using the relationship between mound internal gas concentration and flux from one species to predict mound fluxes from other termite species (as has been done in past) would result in errors of more than 5-fold for CH4 and 3-fold for CO2. 5. This study highlights that CO2 fluxes from termite mounds are generally more than one order of magnitude greater than CH4 fluxes. There are species-specific relationships between CH4 and CO2 fluxes from a~mound, and between the inside mound concentration of a gas and the mound flux emission of the same gas, but these relationships vary greatly among termite species. Consequently, there is no generic relationship that will allow for the prediction of CH4 fluxes from termite mounds of all species.

Investigating CH4 production in an oxic plant-soil system -a new approach combining isotopic labelling (13C) and inhibitors

NASA Astrophysics Data System (ADS)

Lenhart, Katharina; Keppler, Frank

2017-04-01

Typically, aerated soil are net sinks of atmospheric methane (CH4), being highest in native ecosystems (pristine forests > managed forests > grasslands > crop fields). However, this does not exclude a simultaneous endogenic CH4 production in the plant-soil system, which cannot be detected simply via CH4 flux measurements. Methanogenic archaea producing CH4 under anoxic conditions were thought to be the only biotic source of CH4 in the soil. However, until recently a non-archaeal pathway of CH4 formation is known where CH4 is produced under oxic conditions in plants (Keppler et al. 2006) and fungi (Lenhart et al. 2012). Additionally, abiotic formation of CH4 from soil organic matter was reported (Jugold et al. 2012) and may be ubiquitous in terrestrial ecosystems. The major goal of this project was to determine soil endogenic CH4 sources and to estimate their contribution to the endogenic CH4 production. Especially the effect of plants and fungi on soil CH4 production was investigated. Therefore, a series of experiments was carried out on field fresh soil collected in a grassland and a forest ecosystem under controlled laboratory conditions. By combining selective inhibitors and 13C labelling, CH4 production rates of several CH4 sources were quantified. The major difficulty was to detect the comparatively small flux of CH4 production against the background of the high CH4 consumption rates due to methanotrophic bacteria. Therefore, we supplemented bare soil and soil with vegetation with selective inhibitors and 13C labelled substrates in a closed chamber system. In a first step, CH4 production was determined by the inhibition of CH4 oxidizing bacteria with Difluoromethane (DFM, 2ml l-1). In the following, a 13C labelled substrate (either CO2, Acetate, or Methionine -S-CH3 labelled) was added in combination with a specific inhibitor -either for archaeal methanogenesis (Bromoethanesulfonate), bacteria (Streptomycin), or fungi (Captan, Cycloheximide). Gas samples were

Atmospheric CH4 oxidation by Arctic permafrost and mineral cryosols as a function of water saturation and temperature.

PubMed

Stackhouse, B; Lau, M C Y; Vishnivetskaya, T; Burton, N; Wang, R; Southworth, A; Whyte, L; Onstott, T C

2017-01-01

The response of methanotrophic bacteria capable of oxidizing atmospheric CH 4 to climate warming is poorly understood, especially for those present in Arctic mineral cryosols. The atmospheric CH 4 oxidation rates were measured in microcosms incubated at 4 °C and 10 °C along a 1-m depth profile and over a range of water saturation conditions for mineral cryosols containing type I and type II methanotrophs from Axel Heiberg Island (AHI), Nunavut, Canada. The cryosols exhibited net consumption of ~2 ppmv CH 4 under all conditions, including during anaerobic incubations. Methane oxidation rates increased with temperature and decreased with increasing water saturation and depth, exhibiting the highest rates at 10 °C and 33% saturation at 5 cm depth (260 ± 60 pmol CH 4 gdw -1 d -1 ). Extrapolation of the CH 4 oxidation rates to the field yields net CH 4 uptake fluxes ranging from 11 to 73 μmol CH 4  m -2 d -1 , which are comparable to field measurements. Stable isotope mass balance indicates ~50% of the oxidized CH 4 is incorporated into the biomass regardless of temperature or saturation. Future atmospheric CH 4 uptake rates at AHI with increasing temperatures will be determined by the interplay of increasing CH 4 oxidation rates vs. water saturation and the depth to the water table during summer thaw. © 2016 John Wiley & Sons Ltd.

The Regulation of CH4 and N2O fluxes by Wetlands at Landscape Level

NASA Astrophysics Data System (ADS)

Soosaar, K.; Maddison, M.; Salm, J. O.; Järveoja, J.; Hansen, R.; Mander, Ü.

2012-04-01

The world's wetlands, despite being only about 5% of the terrestrial landscape, are currently significant net sinks of more than 1 Pg yr-1 of carbon (Mitsch et al 2012). At landscape level wetlands and riparian zones are important regulators of nutrient transport (Zedler 2003). However, they can be also significant hot spots of greenhouse gas (GHG) emissions (Teiter&Mander 2005). Swedish experience shows that the nationally planned wetland creation (12,000 ha) could make a significant contribution to the targeted reduction of N fluxes (up to 27% of the Swedish environmental objective), at an environmental risk equalling 0.04% of the national anthropogenic GHG emission (Thiere et al 2011). Only few studies consider the potential GHG emission throughout both natural and created wetlands. The main objective of this study was to clarify the potential of various wetland ecosystem and riparian zones of northern rural landscapes in regulation of GHG emissions. Monthly-based measurements of GHG emissions using closed chamber method were performed from October 2007 to October 2011 in 47 study sites in Estonia. The study sites cover various wetlands and riparian forests as well as reference areas on automorphic soils. In general, wetlands' drainage was the most significant disturbance factor influencing GHG fluxes, causing significant increase of N2O emission as well as decreasing CH4 emission. However, we also observed significantly high CH4 flux from drained peatlands. In most of the soils with ground/soil water levels deeper than 30 cm from the surface, a significant decrease of CH4 fluxes were detected. The highest CH4 emissions (up to 5060 kg CH4-C ha-1 yr-1) were detected from drained fen grasslands. In the case of N2O, no clear differences were found between colder and warmer periods. Relatively higher N2O fluxes were measured from the drained fen grassland, the fertilized arable land, the riparian forest on automorphic soil, and the drained transition fen forest

Verification of CH4 on Mars and investigation of its temporal and spatial variations by SOFIA/EXES

NASA Astrophysics Data System (ADS)

Aoki, Shohei

2015-10-01

Discovery of CH4 in the Martian atmosphere has led to much discussion since it could be a signature of on-going and/or past biological/geological activities on Mars. However, the presence of CH4 and its temporal and spatial variations are still under discussion because previous observations had large uncertainties. We propose sensitive measurements of the Martian CH4 by SOFIA/EXES in order to verify the presence and investigate its temporal and spatial variation. Our primal goal is to demonstrate the firm detection of CH4 on Mars. SOFIA/EXES allows us to perform sensitive observations of the Martian CH4 from the Earth using the 7.5 um band. The high altitude of SOFIA telescope (~12 km) enables us to significantly reduce the effects of terrestrial atmosphere, and high spectral resolution of EXES (R~90,000) enables us to detect the tiny lines of the Martian CH4. We request to perform weekly observations of CH4 by SOFIA/EXES during larger Doppler-shift period (between Feb./2016-March/2016). The large Doppler shift (-14.3 - -17.3 km/s) allows us to separate the Martian and terrestrial CH4 lines. In addition, owing to the relatively large diameter of the SOFIA telescope (~ 2.5 m), geographical distribution of CH4 (3 x 3 areas over the Martian disk) can be investigated. Last but not least, we plan to perform joint observations with (1) the spacecraft-borne MEX/PFS, (2) the ground-based T60/MILAHI, (3) ground-based IRTF/CSHELL, and (4) in-situ Curiosity/TLS. Combination of the current best instruments for the joint observations provide definitive confirmation of the presence (or absence) of CH4, and clues to search for the source.

The magnitude and persistence of soil NO, N20, CH4, and C02 fluxes from burned tropical savanna in Brazil

Treesearch

Mark Poth; Iris Cofman Anderson; Heloisa Sinatora Miranda; Antonia Carlos Miranda; Philip J. Riggan

1995-01-01

Among all global ecosystems, tropical savannas are the most severely and extensively affected by anthropogenic burning. Frequency of fire in cerrado, a type of tropical savanna covering 25% of Brazil, is 2 to 4 years. In 1992 we measured soil fluxes of NO, N20, CH4, and C02 from cerrado sites that had...

Vibrational energy levels for CH4 from an ab initio potential

NASA Technical Reports Server (NTRS)

Schwenke, D. W.; Partridge, H.

2001-01-01

Many areas of astronomy and astrophysics require an accurate high temperature spectrum of methane (CH4). The goal of the present research is to determine an accurate ab initio potential energy surface (PES) for CH4. As a first step towards this goal, we have determined a PES including up to octic terms. We compare our results with experiment and to a PES based on a quartic expansion. Our octic PES gives good agreement with experiment for all levels, while the quartic PES only for the lower levels.

Methods of editing cloud and atmospheric layer affected pixels from satellite data

NASA Technical Reports Server (NTRS)

Nixon, P. R.; Wiegand, C. L.; Richardson, A. J.; Johnson, M. P. (Principal Investigator)

1982-01-01

Subvisible cirrus clouds (SCi) were easily distinguished in mid-infrared (MIR) TIROS-N daytime data from south Texas and northeast Mexico. The MIR (3.55-3.93 micrometer) pixel digital count means of the SCi affected areas were more than 3.5 standard deviations on the cold side of the scene means. (These standard deviations were made free of the effects of unusual instrument error by factoring out the Ch 3 MIR noise on the basis of detailed examination of noisy and noise-free pixels). SCi affected areas in the IR Ch 4 (10.5-11.5 micrometer) appeared cooler than the general scene, but were not as prominent as in Ch 3, being less than 2 standard deviations from the scene mean. Ch 3 and 4 standard deviations and coefficients of variation are not reliable indicators, by themselves, of the presence of SCi because land features can have similar statistical properties.

Effects of permafrost thaw on CO2 and CH4 exchange in a western Alaska peatland chronosequence

USGS Publications Warehouse

Carmel E. Johnston,; Stephanie A. Ewing,; Harden, Jennifer W.; Ruth K. Varner,; Wickland, Kimberly P.; Koch, Joshua C.; Fuller, Christopher C.; Manies, Kristen L.; M. Torre Jorgenson,

2014-01-01

Permafrost soils store over half of global soil carbon (C), and northern frozen peatlands store about 10% of global permafrost C. With thaw, inundation of high latitude lowland peatlands typically increases the surface-atmosphere flux of methane (CH4), a potent greenhouse gas. To examine the effects of lowland permafrost thaw over millennial timescales, we measured carbon dioxide (CO2) and CH4 exchange along sites that constitute a ~1000 yr thaw chronosequence of thermokarst collapse bogs and adjacent fen locations at Innoko Flats Wildlife Refuge in western Alaska. Peak CH4exchange in July (123 ± 71 mg CH4–C m−2 d−1) was observed in features that have been thawed for 30 to 70 (<100) yr, where soils were warmer than at more recently thawed sites (14 to 21 yr; emitting 1.37 ± 0.67 mg CH4–C m−2 d−1 in July) and had shallower water tables than at older sites (200 to 1400 yr; emitting 6.55 ± 2.23 mg CH4–C m−2 d−1 in July). Carbon lost via CH4 efflux during the growing season at these intermediate age sites was 8% of uptake by net ecosystem exchange. Our results provide evidence that CH4 emissions following lowland permafrost thaw are enhanced over decadal time scales, but limited over millennia. Over larger spatial scales, adjacent fen systems may contribute sustained CH4 emission, CO2 uptake, and DOC export. We argue that over timescales of decades to centuries, thaw features in high-latitude lowland peatlands, particularly those developed on poorly drained mineral substrates, are a key locus of elevated CH4 emission to the atmosphere that must be considered for a complete understanding of high latitude CH4 dynamics.

Evaluating Impacts of CO2 and CH4 Gas Intrusion into an Unconsolidated Aquifer: Fate of As and Cd

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lawter, Amanda R.; Qafoku, Nikolla; Shao, Hongbo

2015-07-10

Abstract The sequestration of carbon dioxide (CO2) in deep underground reservoirs has been identified as an important strategy to decrease atmospheric CO2 levels and mitigate global warming, but potential risks on overlying aquifers currently lack a complete evaluation. In addition to CO2, other gases such as methane (CH4) may be present in storage reservoirs. This paper explores for the first time the combined effect of leaking CO2 and CH4 gasses on the fate of major, minor and trace elements in an aquifer overlying a potential sequestration site. Emphasis is placed on the fate of arsenic (As) and cadmium (Cd) releasedmore » from the sediments or present as soluble constituents in the leaking brine. Results from macroscopic batch and column experiments show that the presence of CH4 (at a concentration of 1 % in the mixture CO2/CH4) does not have a significant effect on solution pH or the concentrations of most major elements (such as Ca, Ba, and Mg). However, the concentrations of Mn, Mo, Si and Na are inconsistently affected by the presence of CH4 (i.e., in at least one sediment tested in this study). Cd is not released from the sediments and spiked Cd is mostly removed from the aqueous phase most likely via adsorption. The fate of sediment associated As [mainly sorbed arsenite or As(III) in minerals] and spiked As [i.e., As5+] is complex. Possible mechanisms that control the As behavior in this system are discussed in this paper. Results are significant for CO2 sequestration risk evaluation and site selection and demonstrate the importance of evaluating reservoir brine and gas stream composition during site selection to ensure the safest site is being chosen.« less

Theoretical Investigations of CO2 and CH4 Sorption in an Interpenetrated Diamondoid Metal–Organic Material

PubMed Central

2015-01-01

Grand canonical Monte Carlo (GCMC) simulations of CO2 and CH4 sorption and separation were performed in dia-7i-1-Co, a metal–organic material (MOM) consisting of a 7-fold interpenetrated net of Co2+ ions coordinated to 4-(2-(4-pyridyl)ethenyl)benzoate linkers. This MOM shows high affinity toward CH4 at low loading due to the presence of narrow, close fitting, one-dimensional hydrophobic channels—this makes the MOM relevant for applications in low-pressure methane storage. The calculated CO2 and CH4 sorption isotherms and isosteric heat of adsorption, Qst, values in dia-7i-1-Co are in good agreement with the corresponding experimental results for all state points considered. The experimental initial Qst value for CH4 in dia-7i-1-Co is currently the highest of reported MOM materials, and this was further validated by the simulations performed herein. The simulations predict relatively constant Qst values for CO2 and CH4 sorption across all loadings in dia-7i-1-Co, consistent with the one type of binding site identified for the respective sorbate molecules in this MOM. Examination of the three-dimensional histogram showing the sites of CO2 and CH4 sorption in dia-7i-1-Co confirmed this finding. Inspection of the modeled structure revealed that the sorbate molecules form a strong interaction with the organic linkers within the constricted hydrophobic channels. Ideal adsorbed solution theory (IAST) calculations and GCMC binary mixture simulations predict that the selectivity of CO2 over CH4 in dia-7i-1-Co is quite low, which is a direct consequence of the MOM’s high affinity toward both CO2 and CH4 as well as the nonspecific mechanism shown here. This study provides theoretical insights into the effects of pore size on CO2 and CH4 sorption in porous MOMs and its effect upon selectivity, including postulating design strategies to distinguish between sorbates of similar size and hydrophobicity. PMID:24835550

The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures

NASA Astrophysics Data System (ADS)

Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

2016-09-01

Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H2) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H2/CH4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of <40 for biotic methane. The definition of the criterion was based on two serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311-500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H2/CH4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H2/CH4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400-500 °C, the H2/CH4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H2/CH4 ratios cannot reliably discriminate abiotic from biotic methane.

Stratospheric CH4 and CO2 profiles derived from SCIAMACHY solar occultation measurements

NASA Astrophysics Data System (ADS)

Noël, S.; Bramstedt, K.; Hilker, M.; Liebing, P.; Plieninger, J.; Reuter, M.; Rozanov, A.; Bovensmann, H.; Burrows, J. P.

2015-11-01

Stratospheric profiles of methane (CH4) and carbon dioxide (CO2) have been derived from solar occultation measurements of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). The retrieval is performed using a method called "Onion Peeling DOAS" (ONPD) which combines an onion peeling approach with a weighting function DOAS (Differential Optical Absorption Spectroscopy) fit. By use of updated pointing information and optimisation of the data selection and of the retrieval approach the altitude range for reasonable CH4 could be extended to about 17 to 45 km. Furthermore, the quality of the derived CO2 has been assessed such that now the first stratospheric profiles of CO2 from SCIAMACHY are available. Comparisons with independent data sets yield an estimated accuracy of the new SCIAMACHY stratospheric profiles of about 5-10 % for CH4 and 2-3 % for CO2. The accuracy of the products is currently mainly restricted by the appearance of unexpected vertical oscillations in the derived profiles which need further investigation. Using the improved ONPD retrieval, CH4 and CO2 stratospheric data sets covering the whole SCIAMACHY time series (August 2002-April 2012) and the latitudinal range between about 50 and 70° N have been derived. Based on these time series, CH4 and CO2 trends have been estimated, which are in reasonable agreement with total column trends for these gases. This shows that the new SCIAMACHY data sets can provide valuable information about the stratosphere.

The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures

PubMed Central

Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

2016-01-01

Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H2) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H2/CH4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of <40 for biotic methane. The definition of the criterion was based on two serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311–500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H2/CH4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H2/CH4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400–500 °C, the H2/CH4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H2/CH4 ratios cannot reliably discriminate abiotic from biotic methane. PMID:27666288

The H2/CH4 ratio during serpentinization cannot reliably identify biological signatures.

PubMed

Huang, Ruifang; Sun, Weidong; Liu, Jinzhong; Ding, Xing; Peng, Shaobang; Zhan, Wenhuan

2016-09-26

Serpentinization potentially contributes to the origin and evolution of life during early history of the Earth. Serpentinization produces molecular hydrogen (H 2 ) that can be utilized by microorganisms to gain metabolic energy. Methane can be formed through reactions between molecular hydrogen and oxidized carbon (e.g., carbon dioxide) or through biotic processes. A simple criterion, the H 2 /CH 4 ratio, has been proposed to differentiate abiotic from biotic methane, with values approximately larger than 40 for abiotic methane and values of <40 for biotic methane. The definition of the criterion was based on two serpentinization experiments at 200 °C and 0.3 kbar. However, it is not clear whether the criterion is applicable at a wider range of temperatures. In this study, we performed sixteen experiments at 311-500 °C and 3.0 kbar using natural ground peridotite. Our results demonstrate that the H 2 /CH 4 ratios strongly depend on temperature. At 311 °C and 3.0 kbar, the H 2 /CH 4 ratios ranged from 58 to 2,120, much greater than the critical value of 40. By contrast, at 400-500 °C, the H 2 /CH 4 ratios were much lower, ranging from 0.1 to 8.2. The results of this study suggest that the H 2 /CH 4 ratios cannot reliably discriminate abiotic from biotic methane.

H atoms in CH4 and Xe matrices at cryogenic temperatures

NASA Astrophysics Data System (ADS)

Willard, J. E.

1982-07-01

Cryogenic techniques coupled with electron spin resonance detection methods have made it possible to produce long-lived trapped hydrogen atoms in inert matrices at 4 K and to study their reactions with neutral molecules and molecular fragments when the temperature is raised to the point where they diffuse. Under the matrix conditions H atoms abstract H rapidly from all carbon-hydrogen bonds (except those of CH 4) by quantum mechanical tunnelling, even though such reactions would be precluded if the classical activation energy prevailed. Thermal H atoms in CH 4 at 15 K add to CO to form the HCO radical, and to O 2 to form the HO 2 radical. When exposed to the appropriate wavelength of light these and other radicals, including CH 3, C 2H 5 and C 2H 3 lose H by photoelimination. The H atoms are produced in the matrices by X radiolysis, γ-ray radiolysis, or photolysis of a hydrogen halide. This paper reviews some of the most significant current findings in the field from different laboratories.

Seasonal CH4 and N2O emissions and plant growth characteristics of several cultivars in direct seeded rice systems

NASA Astrophysics Data System (ADS)

Simmonds, M.; Anders, M. M.; Adviento-Borbe, M. A.; Van Kessel, C.; McClung, A.; Linquist, B.

2014-12-01

Understanding cultivar effects on field greenhouse gas (GHG) emissions in rice (Oryza sativa L.) systems is needed to improve the accuracy of predictive models used for estimating GHG emissions, and to determine to what extent choice of cultivar may have on GHG mitigation. We compared CH4 and N2O emissions, global warming potential (GWP = N2O + CH4), yield-scaled GWP (GWPY = GWP Mg-1 grain), and plant growth characteristics of 8 cultivars within 4 study sites in California and Arkansas. Seasonal CH4 emissions differed between cultivars by a factor of 2.1 and 1.3 at one California and one Arkansas site, respectively. Nitrous oxide emissions were negligible, comprised <10% of GWP, and were not different among cultivars. When sites and cultivars were pooled, and data were normalized to site averages, there was a positive correlation (r = 0.33) between root biomass at heading and seasonal CH4 emissions, but no correlation with shoot biomass at heading, or grain or straw biomass at maturity. Although differences in GWP and GWPY were observed, the consistency of some of the trends was variable across sites, indicating the importance of the genotype x environment interaction. While no high-yielding and low CH4-emitting cultivars were identified at the California sites, among the Southern varieties tested at the Arkansas site, the lowest emitting cultivar had the highest yield. This highlights the potential for breeding high-yielding varieties with low GWP, the ideal scenario to achieve low GWPY due to simultaneously mitigating GHG emissions and improving global food security.

From California dreaming to California data: Challenging historic models for landfill CH4 emissions

USDA-ARS?s Scientific Manuscript database

Improved quantification of diverse CH4 sources at the urban scale is needed to guide local greenhouse gas (GHG) mitigation strategies in the Anthropocene. Herein, we focus on landfill CH4 emissions in California, challenging the current IPCC methodology which focuses on a climate dependency for land...

Measuring the Impact of Rising CO2 and CH4 on the Surface Energy Balance

NASA Astrophysics Data System (ADS)

Feldman, D.; Collins, W.; Biraud, S.; Turner, D. D.; Mlawer, E. J.; Gero, P. J.; Xie, S.; Shippert, T.; Torn, M. S.

2015-12-01

We use observations at the North Slope of Alaska (NSA) and Southern Great Plains (SGP) ARM sites to improve understanding both of the distribution of CO2 and CH4and their influence on the surface energy balance. We use aircraft and ground-based in situ data to characterize the temporal distribution of these greenhouse gases, and spectroscopic observations to derive their collocated surface radiative forcing. The spectroscopically-measured surface radiative forcing from rising CO2 is 0.2 W/m2/decade at both sites, with a seasonal cycle of 0.2 W/m2. This finding is largely consistent with theoretical predictions, providing robust evidence of radiative perturbations to the Earth's surface energy budget due to anthropogenic influences. The contribution from CH4 to the surface energy balance is more spatially and temporally heterogeneous. The ground-based measurements of CH4 at NSA and SGP indicate rising atmospheric concentrations except for a hiatus from 1995-2005, while more recent aircraft profiles indicate that concentrations in the boundary layer and free troposphere are correlated at NSA and decorrelated at SGP. The probability density functions of boundary layer concentrations of CH4 at NSA show little skew, but at SGP show positive skewness, which increased with the introduction of nearby fossil-fuel extraction. The correlated increases in atmospheric measurements of C2H6 and CH4that only occur at SGP are consistent with an anthropogenic influence there. Time-series of spectroscopically-measured CH4 surface radiative forcing at SGP and NSA also indicate positive trends of 0.1 W/m2/decade associated with the end of the hiatus, marked seasonal cycles, and little skew at NSA and a positive skew at SGP. The combination of in situ and spectroscopic measurements at these sites enables the quantification of surface radiative forcing from anthropogenic CH4. Implications are discussed for how advanced spectroscopic remote sensing measurements of CH4 can be used to

NO(y) Correlation with N2O and CH4 in the Midlatitude Stratosphere

NASA Technical Reports Server (NTRS)

Kondo, Y.; Schmidt, U.; Sugita, T.; Engel, A.; Koike, M.; Aimedieu, P.; Gunson, M. R.; Rodriguez, J.

1996-01-01

Total reactive nitrogen (NO(y)), nitrous oxide (NO2), methane (CH4), and ozone (03) were measured on board a balloon launched from Aire sur l'Adour (44 deg N, 0 deg W), France on October 12, 1994. Generally, NO(y) was highly anti-correlated with N2O and CH4 at altitudes between 15 and 32 km. The linear NO(y) - N2O and NO(y) - CH4 relationships obtained by the present observations are very similar to those obtained on board ER-2 and DC-8 aircraft previously at altitude below 20 km in the northern hemisphere. They also agree well with the data obtained by the Atmospheric Trace Molecule Spectroscopy (ATMOS) instrument at 41 deg N in November 1994. Slight departures from linear correlations occurred around 29 km, where N2O and CH4 mixing ratios were larger than typical midlatitude values, suggesting horizontal transport of tropical airmasses to northern midlatitudes in a confined altitude region.

Recent Experiments Leading to the Characterization of the Performance of Portable (He-Ne)/CH4 Lasers: Part II: Results of the 1986 LPTF Absolute Frequency Measurements

NASA Astrophysics Data System (ADS)

Clairon, A.; Dahmani, B.; Acef, O.; Granveaud, M.; Domnin, Yu S.; Pouchkine, S. B.; Tatarenkov, V. M.; Felder, R.

1988-01-01

Comparison of the VNIIFTRI and LPTF frequency multiplication chains has been carried out through the measurement of the frequency of a portable VNIIFTRI (He-Ne)/CH4 laser. Agreement is within 100 Hz (1.1 parts in 1012) and is secured by the very good medium-term frequency repeatability of the (He-Ne)/CH4 VNIIFTRI portable laser (a few parts in 1013). On the same occasion a measurement of the frequency of the BIPM (He-Ne)/CH4 reference laser (B.3) has been performed at LPTF. Other experiments carried out on the BIPM laser show that the reproducibility of the (He-Ne)/CH4 system could be improved by a systematic study and then by a better control of the various perturbing factors which influence the shape of the methane-saturated absorption peak.

Year-round CH4 and CO2 flux dynamics in two contrasting freshwater ecosystems of the subarctic

NASA Astrophysics Data System (ADS)

Jammet, Mathilde; Dengel, Sigrid; Kettner, Ernesto; Parmentier, Frans-Jan W.; Wik, Martin; Crill, Patrick; Friborg, Thomas

2017-11-01

Lakes and wetlands, common ecosystems of the high northern latitudes, exchange large amounts of the climate-forcing gases methane (CH4) and carbon dioxide (CO2) with the atmosphere. The magnitudes of these fluxes and the processes driving them are still uncertain, particularly for subarctic and Arctic lakes where direct measurements of CH4 and CO2 emissions are often of low temporal resolution and are rarely sustained throughout the entire year. Using the eddy covariance method, we measured surface-atmosphere exchange of CH4 and CO2 during 2.5 years in a thawed fen and a shallow lake of a subarctic peatland complex. Gas exchange at the fen exhibited the expected seasonality of a subarctic wetland with maximum CH4 emissions and CO2 uptake in summer, as well as low but continuous emissions of CH4 and CO2 throughout the snow-covered winter. The seasonality of lake fluxes differed, with maximum CO2 and CH4 flux rates recorded at spring thaw. During the ice-free seasons, we could identify surface CH4 emissions as mostly ebullition events with a seasonal trend in the magnitude of the release, while a net CO2 flux indicated photosynthetic activity. We found correlations between surface CH4 emissions and surface sediment temperature, as well as between diel CO2 uptake and diel solar input. During spring, the breakdown of thermal stratification following ice thaw triggered the degassing of both CH4 and CO2. This spring burst was observed in 2 consecutive years for both gases, with a large inter-annual variability in the magnitude of the CH4 degassing. On the annual scale, spring emissions converted the lake from a small CO2 sink to a CO2 source: 80 % of total annual carbon emissions from the lake were emitted as CO2. The annual total carbon exchange per unit area was highest at the fen, which was an annual sink of carbon with respect to the atmosphere. Continuous respiration during the winter partly counteracted the fen summer sink by accounting for, as both CH4 and CO2, 33

A Time-Dependent Quantum Dynamics Study of the H2 + CH3 yields H + CH4 Reaction

NASA Technical Reports Server (NTRS)

Wang, Dunyou; Kwak, Dochan (Technical Monitor)

2002-01-01

We present a time-dependent wave-packet propagation calculation for the H2 + CH3 yields H + CH4 reaction in six degrees of freedom and for zero total angular momentum. Initial state selected reaction probability for different initial rotational-vibrational states are presented in this study. The cumulative reaction probability (CRP) is obtained by summing over initial-state-selected reaction probability. The energy-shift approximation to account for the contribution of degrees of freedom missing in the 6D calculation is employed to obtain an approximate full-dimensional CRP. Thermal rate constant is compared with different experiment results.

Simulations and experimental investigations of the competitive adsorption of CH4 and CO2 on low-rank coal vitrinite.

PubMed

Yu, Song; Bo, Jiang; Jiahong, Li

2017-09-16

The mechanism for the competitive adsorption of CH 4 and CO 2 on coal vitrinite (DV-8, maximum vitrinite reflectance R o,max  = 0.58%) was revealed through simulation and experimental methods. A saturated state was reached after absorbing 17 CH 4 or 22 CO 2 molecules per DV-8 molecule. The functional groups (FGs) on the surface of the vitrinite can be ranked in order of decreasing CH 4 and CO 2 adsorption ability as follows: [-CH 3 ] > [-C=O] > [-C-O-C-] > [-COOH] and [-C-O-C-] > [-C=O] > [-CH 3 ] > [-COOH]. CH 4 and CO 2 distributed as aggregations and they were both adsorbed at the same sites on vitrinite, indicating that CO 2 can replace CH 4 by occupying the main adsorption sites for CH 4 -vitrinite. High temperatures are not conducive to the adsorption of CH 4 and CO 2 on vitrinite. According to the results of density functional theory (DFT) and grand canonical Monte Carlo (GCMC) calculations, vitrinite has a higher adsorption capacity for CO 2 than for CH 4 , regardless of whether a single-component or binary adsorbate is considered. The equivalent adsorption heat (EAH) of CO 2 -vitrinite (23.02-23.17) is higher than that of CH 4 -vitrinite (9.04-9.40 kJ/mol). The EAH of CO 2 -vitrinite decreases more rapidly with increasing temperature than the EAH of CH 4 -vitrinite does, indicating in turn that the CO 2 -vitrinite bond weakens more quickly with increasing temperature than the CH 4 -vitrinite bond does. Simulation data were found to be in good accord with the corresponding experimental results.

Distinct Anaerobic Bacterial Consumers of Cellobiose-Derived Carbon in Boreal Fens with Different CO2/CH4 Production Ratios

PubMed Central

Eiler, Alexander; Biasi, Christina; Tuittila, Eeva-Stiina; Yrjälä, Kim; Fritze, Hannu

2016-01-01

ABSTRACT Northern peatlands in general have high methane (CH4) emissions, but individual peatlands show considerable variation as CH4 sources. Particularly in nutrient-poor peatlands, CH4 production can be low and exceeded by carbon dioxide (CO2) production from unresolved anaerobic processes. To clarify the role anaerobic bacterial degraders play in this variation, we compared consumers of cellobiose-derived carbon in two fens differing in nutrient status and the ratio of CO2 to CH4 produced. After [13C]cellobiose amendment, the mesotrophic fen produced equal amounts of CH4 and CO2. The oligotrophic fen had lower CH4 production but produced 3 to 59 times more CO2 than CH4. RNA stable-isotope probing revealed that in the mesotrophic fen with higher CH4 production, cellobiose-derived carbon was mainly assimilated by various recognized fermenters of Firmicutes and by Proteobacteria. The oligotrophic peat with excess CO2 production revealed a wider variety of cellobiose-C consumers, including Firmicutes and Proteobacteria, but also more unconventional degraders, such as Telmatobacter-related Acidobacteria and subphylum 3 of Verrucomicrobia. Prominent and potentially fermentative Planctomycetes and Chloroflexi did not appear to process cellobiose-C. Our results show that anaerobic degradation resulting in different levels of CH4 production can involve distinct sets of bacterial degraders. By distinguishing cellobiose degraders from the total community, this study contributes to defining anaerobic bacteria that process cellulose-derived carbon in peat. Several of the identified degraders, particularly fermenters and potential Fe(III) or humic substance reducers in the oligotrophic peat, represent promising candidates for resolving the origin of excess CO2 production in peatlands. IMPORTANCE Peatlands are major sources of the greenhouse gas methane (CH4), yet in many peatlands, CO2 production from unresolved anaerobic processes exceeds CH4 production. Anaerobic

Distinct Anaerobic Bacterial Consumers of Cellobiose-Derived Carbon in Boreal Fens with Different CO2/CH4 Production Ratios.

PubMed

Juottonen, Heli; Eiler, Alexander; Biasi, Christina; Tuittila, Eeva-Stiina; Yrjälä, Kim; Fritze, Hannu

2017-02-15

Northern peatlands in general have high methane (CH 4 ) emissions, but individual peatlands show considerable variation as CH 4 sources. Particularly in nutrient-poor peatlands, CH 4 production can be low and exceeded by carbon dioxide (CO 2 ) production from unresolved anaerobic processes. To clarify the role anaerobic bacterial degraders play in this variation, we compared consumers of cellobiose-derived carbon in two fens differing in nutrient status and the ratio of CO 2 to CH 4 produced. After [ 13 C]cellobiose amendment, the mesotrophic fen produced equal amounts of CH 4 and CO 2 The oligotrophic fen had lower CH 4 production but produced 3 to 59 times more CO 2 than CH 4 RNA stable-isotope probing revealed that in the mesotrophic fen with higher CH 4 production, cellobiose-derived carbon was mainly assimilated by various recognized fermenters of Firmicutes and by Proteobacteria The oligotrophic peat with excess CO 2 production revealed a wider variety of cellobiose-C consumers, including Firmicutes and Proteobacteria, but also more unconventional degraders, such as Telmatobacter-related Acidobacteria and subphylum 3 of Verrucomicrobia Prominent and potentially fermentative Planctomycetes and Chloroflexi did not appear to process cellobiose-C. Our results show that anaerobic degradation resulting in different levels of CH 4 production can involve distinct sets of bacterial degraders. By distinguishing cellobiose degraders from the total community, this study contributes to defining anaerobic bacteria that process cellulose-derived carbon in peat. Several of the identified degraders, particularly fermenters and potential Fe(III) or humic substance reducers in the oligotrophic peat, represent promising candidates for resolving the origin of excess CO 2 production in peatlands. Peatlands are major sources of the greenhouse gas methane (CH 4 ), yet in many peatlands, CO 2 production from unresolved anaerobic processes exceeds CH 4 production. Anaerobic

Real-time analysis of δ13C- and δD-CH4 in ambient air with laser spectroscopy: Method development and intercomparison

NASA Astrophysics Data System (ADS)

Harris, E. J.; Eyer, S.; Mohn, J.; Röckmann, T.; Popa, E.; Lowry, D.; Nisbet, E. G.; Fisher, R. E.; Brennwald, M. S.; Fischer, H.; Emmenegger, L.; Tuzson, B.; Zellweger, C.

2015-12-01

Methane (CH4) is the second most important anthropogenically emitted greenhouse gas after carbon dioxide (CO2). Its mole fraction has increased from around 722 ppb in pre-industrial times to 1824 ppb in 2013 and the anthropogenic fraction is estimated to be 60 % of the total emissions. A promising approach to improve the understanding of the CH4 budget is the use of isotopologues to distinguish between various CH4 source processes. In the presented study in situ and simultaneous measurement of the three most abundant isotopologues of methane using mid-infrared laser absorption spectroscopy is demonstrated. A field-deployable, autonomous platform is realized by coupling a compact quantum cascade laser absorption spectrometer (QCLAS) to a preconcentration unit, called TRace gas EXtractor (TREX). This unit enhances CH4 mole fractions by a factor of up to 500 above ambient levels and quantitatively separates interfering trace gases such as N2O and CO2. The analytical precision of the QCLAS isotope measurement on the preconcentrated (750 ppm, parts-per-million, mmole/mole) methane is 0.1‰ and 0.5 ‰ for δ13C- and δD-CH4 at 10 min averaging time. [1] Based on replicate measurements of compressed air during a two-week intercomparison campaign, the repeatability of the TREX-QCLAS was determined to be 0.19 ‰ and 1.9 ‰ for δ13C and δD-CH4, respectively. In this intercomparison campaign the new in situ technique is compared to IRMS based on glass flask and bag sampling and real time CH4 isotope analysis by two commercially available laser spectrometers (Figure). Both laser-based analyzers were limited to methane mole fraction and δ13C-CH4 analysis, and only one of them, a cavity ring down spectrometer, was capable to deliver meaningful data for the isotopic composition. After correcting for scale offsets, the average difference between TREX-QCLAS data and bag/flask sampling-IRMS values are within the extended WMO compatibility goals of 0.2 and 5 ‰ for δ13C- and

Seasonal variation in CH4 emissions and production and oxidation potentials at microsites on an oligotrophic pine fen.

PubMed

Saarnio, S; Alm, Jukka; Silvola, Jouko; Lohila, Annalea; Nykänen, Hannu; Martikainen, Pertti J

1997-04-01

 Temporal and spatial variation in CH 4 emissions was studied at hummock, Eriophorum lawn, flark and Carex lawn microsites in an oligotrophic pine fen over the growing season using a static chamber method, and CH 4 production and oxidation potentials in peat profiles from hummock and flark were determined in laboratory incubation experiments. Emissions were lowest in the hummocks, and decreased with increasing hummock height, while in the lawns and flarks they increased with increasing sedge cover. Statistical response functions with water table and peat temperature as independent variables were calculated in order to reconstruct seasonal CH 4 emissions by reference to the time series for peat temperature and water table specific to each microsite type. Mean CH 4 emissions in the whole area in the snow-free period of 1993, weighted in terms of the proportions of the microsites, were 1.7 mol CH 4 m -2 . Potential CH 4 production and oxidation rates were very low in the hummocks rising above the groundwater table, but were relatively similar when expressed per dry weight of peat both in the hummocks and flarks below the water table. The CH 4 production potential increased in autumn at both microsites and CH 4 oxidation potential seemed to decrease. The decrease in temperature in autumn certainly reduced in situ decomposition processes, possibly leaving unused substrates in the peat, which would explain the increase in CH 4 production potential.

Dual stable isotopes of CH4 from Yellowstone hot-springs suggest hydrothermal processes involving magmatic CO2

NASA Astrophysics Data System (ADS)

Moran, James J.; Whitmore, Laura M.; Jay, Zackary J.; Jennings, Ryan deM.; Beam, Jacob P.; Kreuzer, Helen W.; Inskeep, William P.

2017-07-01

Volcanism and post-magmatism contribute significant annual methane (CH4) fluxes to the atmosphere (on par with other natural sources such as forest fire and wild animal emissions) and have been implicated in past climate-change events. The Yellowstone hot spot is one of the largest volcanic systems on Earth and is known to emit CH4 (as well as carbon dioxide (CO2) and other gases), but the ultimate sources of this CH4 flux have not been elucidated. Here we use dual stable isotope analysis (δ2H and δ13C) of CH4 sampled from ten high-temperature geothermal pools in Yellowstone National Park along with other isotopic and gas analyses to evaluate potential sources of methane. The average δ13C and δ2H values of CH4 emitted from hot springs (26.7 (± 2.4) and - 236.9 (± 12.0) ‰, respectively) are inconsistent with microbial methanogenesis but do not allow distinction between thermogenic and abiotic sources. Correlation between δ13CCH4 and δ13C of dissolved inorganic C (DIC) is consistent with DIC as the parent C source for the observed CH4, or with equilibration of CH4 and DIC. Methane formation temperatures estimated by isotopic geothermometry based on δ13CCH4 and δ13CCO2 ranged from 250-350 °C, which is just below previous temperature estimates for the hydrothermal reservoir. Further, the δ2HH2O of the thermal springs and the measured δ2HCH4 values are consistent with equilibration between the source water and the CH4 at the formation temperatures. Though the ultimate origin of the CH4 could be attributed to either abiotic of themorgenic processes with subsequent isotopic equilibration, the C1/C2 + composition of the gases is more consistent with abiotic origins for most of the samples. Thus, our data support the hypothesis that subsurface rock-water interactions are responsible for at least a significant fraction of the CH4 flux from the Yellowstone National Park volcanic system.

Stratospheric CH4 and CO2 profiles derived from SCIAMACHY solar occultation measurements

NASA Astrophysics Data System (ADS)

Noël, Stefan; Bramstedt, Klaus; Hilker, Michael; Liebing, Patricia; Plieninger, Johannes; Reuter, Max; Rozanov, Alexei; Sioris, Christopher E.; Bovensmann, Heinrich; Burrows, John P.

2016-04-01

Stratospheric profiles of methane (CH4) and carbon dioxide (CO2) have been derived from solar occultation measurements of the SCanning Imaging Absorption spectroMeter for Atmospheric CHartographY (SCIAMACHY). The retrieval is performed using a method called onion peeling DOAS (ONPD), which combines an onion peeling approach with a weighting function DOAS (differential optical absorption spectroscopy) fit in the spectral region between 1559 and 1671 nm. By use of updated pointing information and optimisation of the data selection as well as of the retrieval approach, the altitude range for reasonable CH4 could be broadened from 20 to 40 km to about 17 to 45 km. Furthermore, the quality of the derived CO2 has been assessed such that now the first stratospheric profiles (17-45 km) of CO2 from SCIAMACHY are available. Comparisons with independent data sets yield an estimated accuracy of the new SCIAMACHY stratospheric profiles of about 5-10 % for CH4 and 2-3 % for CO2. The accuracy of the products is currently mainly restricted by the appearance of unexpected vertical oscillations in the derived profiles which need further investigation. Using the improved ONPD retrieval, CH4 and CO2 stratospheric data sets covering the whole SCIAMACHY time series (August 2002-April 2012) and the latitudinal range between about 50 and 70° N have been derived. Based on these time series, CH4 and CO2 trends have been estimated. CH4 trends above about 20 km are not significantly different from zero and the trend at 17 km is about 3 ppbv year-1. The derived CO2 trends show a general decrease with altitude with values of about 1.9 ppmv year-1 at 21 km and about 1.3 ppmv year-1 at 39 km. These results are in reasonable agreement with total column trends for these gases. This shows that the new SCIAMACHY data sets can provide valuable information about the stratosphere.

Combining two complementary micrometeorological methods to measure CH4 and N2O fluxes over pasture

NASA Astrophysics Data System (ADS)

Laubach, J.; Barthel, M.; Fraser, A.; Hunt, J. E.; Griffith, D. W. T.

2015-09-01

New Zealand's largest industrial sector is pastoral agriculture, giving rise to a large fraction of the country's emissions of methane (CH4) and nitrous oxide (N2O). We designed a system to continuously measure CH4 and N2O fluxes at the field scale on two adjacent pastures that differed with respect to management. At the core of this system was a closed-cell Fourier-transform infrared spectrometer (FTIR), measuring the mole fractions of CH4, N2O and carbon dioxide (CO2) at two heights at each site. In parallel, CO2 fluxes were measured using eddy-covariance instrumentation. We applied two different micrometeorological ratio methods to infer the CH4 and N2O fluxes from their respective mole fractions and the CO2 fluxes. The first is a variant of the flux-gradient method, where it is assumed that the turbulent diffusivities of CH4 and N2O equal that of CO2. This method was reliable when the CO2 mole-fraction difference between heights was at least 4 times greater than the FTIR's resolution of differences. For the second method, the temporal increases of mole fractions in the stable nocturnal boundary layer, which are correlated for concurrently-emitted gases, are used to infer the unknown fluxes of CH4 and N2O from the known flux of CO2. This method was sensitive to "contamination" from trace gas sources other than the pasture of interest and therefore required careful filtering. With both methods combined, estimates of mean daily CH4 and N2O fluxes were obtained for 60 % of days at one site and 77 % at the other. Both methods indicated both sites as net sources of CH4 and N2O. Mean emission rates for one year at the unfertilised, winter-grazed site were 8.2 (± 0.91) nmol CH4 m-2 s-1 and 0.40 (± 0.018) nmol N2O m-2 s-1. During the same year, mean emission rates at the irrigated, fertilised and rotationally-grazed site were 7.0 (± 0.89) nmol CH4 m-2 s-1 and 0.57 (± 0.019) nmol N2O m-2 s-1. At this site, the N2O emissions amounted to 1.19 (± 0.15) % of the

Combining two complementary micrometeorological methods to measure CH4 and N2O fluxes over pasture

NASA Astrophysics Data System (ADS)

Laubach, Johannes; Barthel, Matti; Fraser, Anitra; Hunt, John E.; Griffith, David W. T.

2016-03-01

New Zealand's largest industrial sector is pastoral agriculture, giving rise to a large fraction of the country's emissions of methane (CH4) and nitrous oxide (N2O). We designed a system to continuously measure CH4 and N2O fluxes at the field scale on two adjacent pastures that differed with respect to management. At the core of this system was a closed-cell Fourier transform infrared (FTIR) spectrometer, which measured the mole fractions of CH4, N2O and carbon dioxide (CO2) at two heights at each site. In parallel, CO2 fluxes were measured using eddy-covariance instrumentation. We applied two different micrometeorological ratio methods to infer the CH4 and N2O fluxes from their respective mole fractions and the CO2 fluxes. The first is a variant of the flux-gradient method, where it is assumed that the turbulent diffusivities of CH4 and N2O equal that of CO2. This method was reliable when the CO2 mole-fraction difference between heights was at least 4 times greater than the FTIR's resolution of differences. For the second method, the temporal increases of mole fractions in the stable nocturnal boundary layer, which are correlated for concurrently emitted gases, are used to infer the unknown fluxes of CH4 and N2O from the known flux of CO2. This method was sensitive to "contamination" from trace gas sources other than the pasture of interest and therefore required careful filtering. With both methods combined, estimates of mean daily CH4 and N2O fluxes were obtained for 56 % of days at one site and 73 % at the other. Both methods indicated both sites as net sources of CH4 and N2O. Mean emission rates for 1 year at the unfertilised, winter-grazed site were 8.9 (±0.79) nmol CH4 m-2 s-1 and 0.38 (±0.018) nmol N2O m-2 s-1. During the same year, mean emission rates at the irrigated, fertilised and rotationally grazed site were 8.9 (±0.79) nmol CH4 m-2 s-1 and 0.58 (±0.020) nmol N2O m-2 s-1. At this site, the N2O emissions amounted to 1.21 (±0.15) % of the nitrogen